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NNadir

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Member since: 2002
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SARSCov2: In silico approach toward identification of unique peptides of viral protein infection.

The paper I'll discuss in this post is this one: In silico approach toward the identification of unique peptides from viral protein infection: Application to COVID-19. It's one of those pre-peer reviewed papers out of BioRxiv.

There's nothing particularly earth shattering about it; it borders on obvious, but not so obvious that anyone would think of doing it: In that sense it's creative. That said, most of the software tools mentioned are public domain, and one could in theory do it at home, which is easy to say, but these authors did do it, and thus are worthy of credit, admiration and appreciation. (It's quite possible that other people have done it as well.)

Most people working in proteomics will be familiar with the tools mentioned therein.

I mention the paper, because it's a nice tutorial on how things work; and is a reflection of the growing power of big data information systems and mass spectrometry, as well as a cheerful reminder that things may not be as bad as one sometimes hears: We have great tools for science, should we not destroy science.

The idea is fairly simple: Do an in silico translation (from the genomic data on the Sars-CoV2 virus) to the coded proteins, then do an in silico enzymatic digestion to find the possible peptides that can be detected by mass spec, eliminate peptides that exhibit cross reactivity with other sequences in endogenous proteins; eliminate those with likely analytical complications; eliminate those that represent genetic instabilities and isoforms, and voila: You have a diagnostic/developmental tool for investigating infection if you also have a nice mass spectrometer.

This graphic from the paper shows the process:



The introduction gives a nice feel for advances. When I was a kid, I used to make analytical tools called "radioimmunoassay assay" (RIA) kits, which involved labeling a species with a radioactive substance (almost always 125-I or more rarely, tritium) and then subjecting it to competitive binding experiments to an antibody to determine the concentration of the analyte. Most young scientists today never used (or necessarily even heard of) RIA kits, although at one time they were "the bee's knees." These were ultimately subsumed by other types of fluorescent/luminescent/electrophotochemical detection systems, the best known being "ELISA," now readily available commercially in monoplex (one protein at a time) and multiplex (lots of proteins at a time) formats. Collectively these systems (including RIA) are known as "ligand binding assays." (LBA).

I will be dead in a few years, but I predict that shortly after I check out of living systems, mass spectrometer will have rendered most LBA systems more or less obsolete, and the authors of the paper suggest as much.

The identification of peptides expressed unique to pathogens is required for the development of diagnostic assays as well as vaccine targets. Antibody based techniques such as enzyme linked immunosorbent assay rely on antibodies raised against specific peptide targets. Mass spectrometry (MS) based diagnostic assays typically require many rounds of optimization to identify peptides that are unique in both sequence or in chemical characteristics to distinguish them from the complex host background.1

The detection of viral proteins in body fluids can be a rapid and specific diagnostic for infection in severe acute respiratory syndrome (SARS).2–4 During the 2003 (SARS) outbreak, non-MS based methods of protein detection proved to be more successful5,6 than LCMS methods.7–9 Non-MS based methods, such as western blots, enzyme-linked immunosorbent assays (ELISAs), and protein arrays, rely on antibodies for the detection of proteins. Given recent studies concerning high variability in antibody production, LCMS-based methods are an attractive alternative approach for the rapid identification of small molecules, proteins, and peptides in clinical settings where consistency is paramount.10,11

In the 15 years since the 2003 SARS outbreak, LCMS technology has experienced a revolution led primarily by increases in the speed, sensitivity, and resolution of MS instruments. Today, protein array and antibody-based methods are falling out of favor in both research and clinical diagnostics, due in large part to the improvements in LCMS technology.12,13 A review of this growth by Grebe and Singh described a clinical lab with no LCMS systems in 1998 that completed over 2 million individual LCMS clinical assays in 2010.14 Incremental improvements in rapid sample preparation techniques, chromatography, and data processing have also contributed to the increasing use of LCMS-based clinical testing. A 2013 study demonstrated the level of advance by identifying 4,000 yeast proteins in one hour of LCMS run time, identifying approximately 75 proteins/min at a rate 100 times faster than studies a decade prior.15


The full paper is open sourced; anyone can read it. It's a little bit technical, but it is a nice overview of how things work for anyone who is interested.

Here's how their in silico analysis worked out:



The caption:

Figure 1.
A summary of the peptide numbers as they are removed from an increasingly complex theoretical proteome background.


Good thinking. Good idea.

If we get a President who doesn't hate science like the racist moron in the office now, we will beat this disease.

Occurrence State and Dissolution Mechanism of Metallic Impurities in Diamond Wire Saw Silicon Powder

The paper I'll discuss in this post is this one: Occurrence State and Dissolution Mechanism of Metallic Impurities in Diamond Wire Saw Silicon Powder (Yang, Wan, Wei, Ma, Wang, ACS Sustainable Chem. Eng. 2020, 8, 33, 12577–12587).

Although it has no bearing on the scientific integrity paper, it begins with a statement that is demonstrably untrue, yet widely believed, one of the two statements to which I have added bold below in the introductory text from the paper. Here is the introduction:

The growing concerns of the traditional energy crisis, the global energy shortage, and pollution associated with the use of traditional energy sources have gradually led to the replacement of the conventional fossil fuel-based energy structure with a renewable energy-based structure.(1−3) Consequently, with the rapid development of the photovoltaic (PV) industry, the demand for solar-grade silicon has increased sharply because of its wide applications as the predominant photoelectric conversion material.(4) Si wafer-based solar cells are the main solar-cell products in the PV industry, accounting for 95% of the total production in 2017.(5,6) The current silicon wafering technology, namely, diamond wire sawing (DWS), has the advantages of a higher feed rate, low surface roughness, and a clear operating environment.(7,8) Diamond wire saw silicon powder (DWSSP) waste is a material generated during DWS. It is a micrometer-sized powder containing numerous metallic contaminants.(9) DWSSP is also considered to be a serious threat to the workplace due to the potential hazards of exothermic oxidation, its highly inflammable properties, and the creation of dust pollution.(10) Like for red mud, the conventional treatment methods for DWSSP, including landfilling and stacking, threaten both human health and the ecosystem due to the complex nature and substantial volume of DWSSP.(11) It is well-known that the selective recovery of metal in multicomponent systems is highly desirable for sustainable metal resource recycling and refractory solid waste treatments,(12) and it is important to develop environmentally friendly processes for the valorization of industrial residues and end-of-life products.(13) Consequently, there is no doubt that the recycling of silicon is both environmentally and economically favorable.(14)


It is simply not true that so called "renewable energy" has replaced, or is replacing, gradually or otherwise, dangerous fossil fuels to any extent at all. The use of dangerous fossil fuels has continuously been growing at an alarming rate since the 20th century through the 21st. In many of my posts here I post a table I prepared from recent editions of the International Energy Agency's World Energy Outlook, which reports on the actual energy consumption of the entire human race.

Here is a table of sources of energy taken from the International Energy Agency’s 2017, 2018, and 2019 Editions of the World Energy Outlook, the last three editions published:



(In this table, I have converted MTOE in the original tables in to the SI unit exajoules in this text.)

World Energy Outlook, 2019

World Energy Outlook, 2018

World Energy Outlook, 2017

Of course, every edition of the World Energy Outlook that I have in my files for this century - probably between 10 and 15, I'm too lazy to look right now - talks about the projected growth of so called "renewable energy" in "scenarios."

I have a few editions from the 20th century, less slick, but more realistic.

The fastest growing source of energy in the 21st century has been coal. For the last year for which data is available, despite all sorts of claims that coal is dying, 2017-2018, the use of coal grew. Mostly this has been driven by China, where they are still debating adding even more coal plants.

Coal grew faster - at 2.97 exajoules for annual growth that year - than did "other renewable energy" which includes solar, wind, geothermal and tidal combined, which grew by 1.63 exajoules in that period.

Despite statements by politicians I enthusiastically support about how many jobs putative "clean energy" will create, it has proved to be the case that the overwhelming majority of the solar cells manufactured, and pretty much everything else, on this planet are manufactured in China.

One reason of course, that China is able to manufacture most of the world's "stuff" is lower worker safety standards, although as the second bold statement in the introduction above.

The second statement in bold in the introduction above lists some of the hazards to workers and to the environment connected with solar PV cell manufacture, these connected with diamond wire saw silicon power, abbreviated DWSSP throughout the rest of the paper. The hazards listed speak for themselves.

These are not, of course, the only hazards associated with PV manufacture. Some are concerned with the fact that the reduction of silicon dioxide - the familiar chemical form of almost all the silicon on Earth, and all naturally occurring silicon - is by heating silicon with carbon. The main source of carbon on this planet is coal.

Silicon is purified by converting it into the liquid trichlorosilane which is then distilled. In 2014, a trichlorosilane distillation plant in the Mie Prefecture of Japan exploded, killing 5 workers instantly and injuring 13.

Of course, industrial accidents happen all the time, and domestic energy accidents do as well - every once in a while one will read about a house exploding and killing people. (Such an explosion killed people near where I live a few years back, and I believe I saw one reported in the media recently.) None of this is remarkable except for maybe this: The trichlorosilane explosion in Mie Prefecture instanteously killed more people than radiation from the destroyed Fukushima nuclear reactors instantaneously killed (zero), and neither event killed as many people as seawater killed.

We couldn't care less how many people are killed by seawater of course, but we never forget if people are merely exposed to industrial radiation while ignoring the fact that people are continuously bathed internally and externally by natural radiation.

Odd world; crazy world; disturbingly crazy world; no wonder it's dying.

The authors of this paper propose to mitigate the hazard of diamond wire saw silicon powder, something they propose to do by removing metals in the powder using strong acids.

To recycle silicon derived from DWSSP, increasing the yield of high-purity silicon is an imperative issue that needs to be resolved.(15) The metallurgical route has become a popular method for silicon purification due to its low cost and environmental friendliness associated with its sustainable process.(16,17) As leaching is the primary and essential stage for the recovery of metals in comparison with pyrometallurgical treatments,(18,19) the metallic impurities present in DWSSP could be removed with a cost-effective compatible acid leaching pretreatment process. Since 2019, several methods have been presented for the purification and recovery of silicon from DWSSP. It is evident that this topic has become a research hotspot and has garnered significant interest from researchers.(20) The authors’ previous studies have investigated the kinetic mechanism of Al removal via HCl leaching,(21) the dissolution and mineralization behavior of metal elements,(22) and the Si core–SiO2 shell structure.(23) Moreover, the kinetic mechanism of iron removal with H2SO4 leaching,(24) multicomponent acid purification,(25) the combined process of slag treatment and acid leaching,(26) and acid leaching followed by induction furnace melting(27) have also been investigated by other research groups...

...In this study, different leaching tests were conducted to reveal the dissolution mechanism of metallic impurities. The common impurities present in DWSSP were sufficiently removed, and two occurrence states of impurities were defined based on their different dissolution behaviors. Moreover, the corresponding dissolution mechanisms were derived...


An issue in these dissolution studies is the formation of silicon dioxide, an unacceptable impurity in solar cells and other silicon devices. This is discussed in the full paper.

Pictures from the paper:



The caption:

Figure 1. SEM characterization of the DWSSP elements mapping: (a) Micro-images for DWSSP′ and (b–g) mapping images for different metallic impurities.


It is important to note that the elements discussed, with the exception of nickel, are not appreciably toxic, however the mode of contact is important. This is dust, and as such the tissue in which it is most likely to be deposited is lung tissue. I personally do not know off hand the effect of reduced silicon in lung tissue, but silicosis, a disease associated with the deposition of silica (silicon dioxide is well known. I suppose one could look up data about these issues, whether something rather like black lung disease is associated, but frankly, I don't think we'd care. Solar energy is "green."

Leaching with hydrochloric acid:



The caption:

Figure 2. Relationships between Al removal and leaching parameters: (a) HCl concentration, (b) leaching temperature, and (c) leaching duration.


Then they get a little nastier, adding an acid mixture close to aqua regia and the scary acid HF. HF dissolves silicon, and in fact, silicon compounds like silica and silica derived products like glass. Presumably the idea is to partially dissolve the silicon to get at the impurities.



The caption:

Figure 3. Impurity removal efficiency of different acid regeants in leach II: (a) the removal efficiency for the different lixiviants and (b) the effect of the HF concentration in the mixed acid solution on the removal efficiency.


The effect on particle size and the changes as suggested by X-ray diffraction.



The caption:

Figure 4. XRD patterns of different materials for the two-stage leaching process (a) the XRD results for DWSSP′ after different leaches and (b) the particle size distribution for DWSSP′ after different leaches.


Silica is an impurity to be avoided of course; the whole point of all this processing is to convert impure silica into pure silicon. This graphic refers to that side product:



The caption:

Figure 6. Silicon and silicon dioxide peak obtained by XPS analysis for the two-stage leaching process: (a) the XPS spectra for DWSSP′ after different leaches and (b) the average SiO2 thicknesses for DWSSP′ after different leaches.


A graphic on the mechanism:



The caption:

Figure 9. Schematic diagrams of the dissolution mechanism and occurrence state of the metallic impurities in DWSSP during the two-stage leaching process.


A cartoon on the proposed process:



The caption:

Figure 10. Recommendation route for silicon recovery from DWSSP


The author's conclusions:

In this study, the occurrence state and dissolution mechanism of metallic impurities in DWSSP during the acid leaching process were determined. The main findings were obtained as follows.

1. The combined process of two-stage acid leaching with 4 M HCl and 2 M HCl + 2.5 M HF was proposed to facilitate the removal of metallic impurities from DWSSP.

2. The leaching results indicated that there are two occurrence states of metallic impurities in the DWSSP. The first type can be easily dissolved in HCl solution, while the elimination of the second type of retained impurities depends on the disintegration of the SiO2 shell, as the SiO2 layer creates a barrier to the dissolution of this type of impurity. For this reason, the removal of metallic impurities can be facilitated via HF addition.

3. The occurrence state of metallic impurities in DWSSP demonstrated the retention of metallic impurities caused by the propagation growth process of the amorphous SiO2 shell. This provides evidence to support the recommended route for the recovery of silicon from DWSSP with an effective acid leaching flow design.


Well then...

I feel like Debby Downer sometimes...

There is a wide spread belief that so called "renewable energy" will save the world. It is of course a kind of cant among us in the Democratic Party, some of us advocating for the "Green New Deal" which is certainly popular among many of us. Regrettably, I argue that the "green new deal" is neither "green" (where "green" is a code word for "sustainable" and "environmentally benign" and "safe" ) nor "new" nor much of a deal, to be honest.

The problem with so called "renewable energy" isn't silicon dust in people's lungs. That's small when compared with the vast death toll associated with the normal use of dangerous fossil fuels. The problem is that it's not working, not even close to working, to address climate change or to ameliorate the vast death toll associated with dangerous fossil fuels. This remains true despite vast cheering, incredible sums of money and huge quantities of matter thrown at it in an almost sacrificial ritual that cannot be stopped because for humanity it has always been an issue that faith can be stronger than reality until at least, reality bites.

Speaking only for myself, I believe reality is biting, big time.

The defining point of my liberalism, and I suspect the liberalism of many others, is that facts matter.

It is a fact that the huge investment in so called "renewable energy" has done nothing to address climate change. Climate change is getting worse, not better. The number of people being killed by dangerous fossil fuel waste, aka "air pollution" remains where it has been for many years, around 19,000 people a day, far more than Covid kills.

A fact..

A fact...

We in the Democratic Party, of course, very much - and rightly so - want to save the world, not only from fascism, because in a fascist world politics trumps science, but also from environmental disaster.

It is not enough to simply push the bad guys out of the way. It is essential to govern well.

Governing well does not include advancing programs that do not work.

In a way, I regret the Republican Party's suicide and its abandonment of principle in favor of personality. A principled opposition makes one stronger, not weaker, because to succeed, one must have one's ideas challenged.

I implore everyone to keep this in mind: Unchallenged ideas don't work very well as ideas, nor, for that matter, as policy.

I wish you a pleasant and relaxing Sunday in these challenging times.

Mitigating the Impact of Thermal Binder Removal for Direct Li-Ion Battery Recycling

The paper I'll discuss in this post is this one: Mitigating the Impact of Thermal Binder Removal for Direct Li-Ion Battery Recycling. (Bradley J. Ross, Michael LeResche, Donghao Liu, Jessica L. Durham, Erik U. Dahl, and Albert L. Lipson,* ACS Sustainable Chem. Eng. 2020, 8, 33, 12511–12515).

There is a widespread belief that energy storage is "green" because the stuff whose massive environmental and technical flaws it's supposed to mitigate, so called "renewable energy," is "green."

Unshakable and persistent faith in these beliefs is destroying the planetary atmosphere, since no amount of energy storage infrastructure built, nor the massive amounts of money and matter thrown at so called "renewable energy" has had any result on the acceleration of climate change or, for that matter, the acceleration of the use of dangerous fossil fuels that mostly drive climate change, or the accumulation of the dangerous fossil fuel waste, carbon dioxide, in that atmosphere which provides most of the mechanism for climate change.

That's a fact. Facts matter.

Whatever.

Happily the paper under discussion reports something that rather pleases me - since I often rail against the criminal social practices (human slavery) that drives the cobalt mining industry - that the amount of cobalt in lithium batteries is being reduced, not eliminated, but at least reduced. That's some good news. The bad news is that it makes the lithium battery industry even less economically viable than it already is - in fact it's not economically viable - meaning that the fate of lithium batteries is going to involve even larger landfills than those with which our party hardy generation has left behind, in total unbridled contempt for all future generations.

There is also widespread belief that hand waving assertions about "recycling" are something other than expressions of this same contempt: In my personal experience, the type most prone to this hand waving are generally bourgeois assholes who want to brag about their stupid solar cells on the roofs of their McMansions powering their Tesla electric car, something they do whenever they are confronted by the reality that in 25 years, all their solar cells and all their batteries are going to be one of the most intractable forms of toxic waste there is, electronic waste, this on a scale of hundreds of millions of tons.

Don't be recklessly brave and head over to the E&E forum to discuss this fact. Facts are not all that impressive there, at least among some of the clientele.

Nevertheless, facts matter. Facts matter.

Another one of the more intractable waste problems the world faces, among many, is the accumulation in the environment of compounds containing the (very strong) carbon fluorine bond. I've written a number of posts in this space about aspects of these compounds, chiefly in connection with perfluoroalkyl sulfonates, carboxylic acids and related compounds. These bonds are also of course, found in Teflon, in a material most of us have utilized in various ways - I have - and they are important components of certain classes of fuel cells, hydrogen fuel cells, where the fluoropolymer Nalfion plays an important role.

It turns out - and I didn't actually know this until yesterday - that fluoropolymers are components of lithium batteries.

That's what this paper is about: Fluoropolymers in lithium batteries.

The introductory cartoon:



From the introduction:

With the introduction of mass-produced electric vehicles, there is a growing need to find appropriate recycling methods before their batteries reach the end of life. Currently, battery recycling is not profitable and is solely reliant on the recovery of the various metals. Cobalt is the most expensive of these metals; therefore, it is the most profitable to recycle. However, cobalt is gradually being eliminated from Li-ion battery cathodes as a way to increase the nickel content, which increases the capacity of the cathode, lowers costs, and reduces reliance on sources of cobalt that utilize poor labor practices.(1−3) The reduction in cobalt content makes processes that only recover the metals less attractive. However, there is still substantial value in the cathode material if it can be recovered in an intact condition.(4) This type of recycling is termed direct recycling, but so far, there have not been any commercially successful processes for direct recycling.

Current battery recycling technology relies on methods that are similar to mining techniques. One such method is the use of pyrometallurgical processing, where the battery materials undergo carbothermal reduction after shredding. One of the byproducts of the this process is a slag, which is often discarded or used as aggregate though Li can be extracted from it.(5) The product of interest is a metal alloy that is refined using a variety of processes, such as hydrometallurgy, which yields high-purity individual metals or metal salts.(6) Another option is to utilize hydrometallurgy directly, which employs acids to dissolve the metals from the battery. These metals are then separated by various processes, and the metals or metal salts can be sold.(7−11)

A direct recycling process for Li-ion batteries requires different unit operations throughout the process to preserve the cathode materials while separating the cathode from other materials. Once the cathode is separated and removed from the aluminum foil, the conductive carbon black and adhesive binders must be removed. Typically, the binder used in lithium-ion batteries to adhere the particles to each other and to the aluminum foil is poly(vinylidene difluoride) (PVDF). Removal of PVDF is required, because relithiation and rejuvenation processes will likely require temperatures that decompose the polymeric binder, and removal allows for simple usage of recycled cathode in current manufacturing processes. Binders can be removed with the use of solvents, mechanical methods,(12) or thermal methods. There have been a number of reports utilizing thermal decomposition to remove binder from various cathode materials. These studies demonstrate the effectiveness of this method to remove PVDF and carbon black, but few report electrochemical performance data.(13−21) Lee et al. have reported the successful removal of PVDF binder from pristine LiNi0.8Mn0.1Co0.1O2 (NMC 811) with good electrochemical performance through the use of annealing at 780 °C without any additions.(14) In order to prevent deleterious effects, the removal of the PVDF and carbon black must be performed in a controlled manner that is optimized for that material. After binder removal, end of life Li-ion battery cathode materials will be partially delithiated.(22) There are a number of methods to relithiate cathode materials including solid state,(23) hydrothermal,(24) and electrochemical processes...(25)


The authors describe the goal (and presumably outcome) of their work:

...To address these challenges, we developed a thermal process that can mitigate the deleterious effects of binder removal through the addition of LiOH·H2O. A thermal process eliminates the need for a large amount of organic solvent that would be needed to adequately remove the binder. Thermogravimetric analysis with mass spectroscopy (TGA-MS) helped with elucidating when the materials are removed and the types of gases evolved during the process. These results were utilized to optimize the processing conditions and demonstrate effective binder removal. Furthermore, this process was extended to both remove binder and relithiate the cathode material in a single step. To understand why this process is effective, X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) were used for analysis.


Some experimental procedures used in the process:

LiNi0.333Mn0.333Co0.333O2 (NMC 111) powder was procured from Toda America Inc. In order to create a consistent delithiated cathode material for testing, chemical delithiation was utilized instead of electrochemical methods. The chemically delithiated NMC 111 was prepared by mixing the cathode in a solution of K2S2O8 at 50 °C for 15 h. The material was then washed with water and filtered followed by acetonitrile washing before drying. Inductively coupled plasma mass spectrometry analysis of the chemically delithiated material indicated that approximately 10% of the lithium was removed.

The electrode materials for binder removal were prepared using methods similar to cathode coating...

...Binder removal experiments were done using a muffle furnace (Nabertherm) with a 200 L/h flow of dry air. The 500 °C processing used a 0.5 °C/min ramp rate and immediate cooling at 2 °C/min. The 925 °C processing used a 0.5 °C/min ramp rate to 500 °C and then 2 °C/min to 925 °C for 8 h before cooling at 2 °C/min. LiOH·H2O (FMC) was ground and sieved using a 45 μm sieve before being acoustically mixed (Resodyn LabRAM II) with the electrode material.


The heat here, of course, requires a lot of energy to recycle materials in this "energy storage" material.

A figure from this text:



The caption:

Figure 1. Thermogravimetric analysis with simultaneous mass spectroscopy of a sample consisting of 92 wt % NMC 111, 3 wt % PVDF, and 5 wt % carbon black.


Do not be deceived by the picoampere scale on the right. In a GC/MS coupled TGA (thermogravimetric analyzer) a tiny sample is thermally decomposed and then a tiny sample of the tiny sample of decomposition gases is injected into the gas chromatograph and detected by the mass spectrometer, the latter being an extremely sensitive device.

One of the decomposition products of the PVDF is unsurprisingly hydrogen fluoride gas.

In my career, when I was still in the lab, I got to work with some pretty hazardous chemicals, chromium VI, lead, mercury, phosgene, a war gas that was responsible for thousands upon thousands of death in the First World War, sodium cyanide, dimethyl sulfate, sodium metal, potassium metal, radioactive iodine, radioactive cobalt (57, not 60) and of course HF, hydrogen fluoride.

In all those years there was one, and only one, occasion where I was truly afraid for my life. Some guys who worked for me came to my office to tell me that a piece of apparatus on which I had worked had leaked pure liquid hydrogen fluoride all over the hood. When I went to look, it was a large amount, and fuming prodigiously. Since I had obviously failed to properly train and properly supervise them, given the outcome, and thus the route responsibility lay with me, I asked them to leave the lab, suited up and cleaned up the mess myself with copious amounts of calcium carbonate. I was literally shaking when I was done.

It was maybe, ten to fifty grams. Some oil refineries use this stuff on a ton scale, as a cracking catalyst. Just saying...

I'm sure that Nalfion manufacturing plants do as well...

And I guess, so do factories, making PVDF for "green" lithium batteries.

Nasty stuff, hydrogen fluoride, scary stuff, in my opinion, far worse than phosgene. (To be perfectly clear, I would recommend its use in nuclear fuel reprocessing, but that's another issue entirely.)

The authors in this paper claim that the hydrogen fluoride gas, however, reacts with the residual metals in the electrode undergoing recycling.

The decomposition products of the PVDF include CO2, H2O, and HF. The signal during the decomposition of PVDF at mass 19, indicating F, is likely HF that splits during the mass spectrometry ionization process. The carbon black then decomposed with the peak of decomposition around 500 °C as indicated by the strong release of CO2. Interestingly, at temperatures exceeding 900 °C, additional fluorine is released, which is accompanied by a mass loss. This is a strong indication that HF reacts with the cathode material. This fluorine release is likely accompanied by lithium loss and phase decomposition at high temperatures that would be expected to release anions from the structure. This is consistent with the weight loss seen at these high temperatures. With this information, we propose the following likely reactions:





So be it. Who am I to say no?

The goal is to directly recycle electrodes, and it is noted that reaction with HF can pull lithium out of the electrode, thus degrading its performance. Therefore the authors add quantities of lithium hydroxide to the reaction to prevent this from happening.

Hence the following figure:



The caption:

Figure 2. Electrochemical cycling rate performance between 2.7 and 4.3 V of NMC 111 cathode that was mixed with 3 wt % PVDF and 5 wt % carbon black, and then had these materials removed at 500 °C with or without added LiOH·H2O.


The performance of electrodes under various conditions:



The caption:

Figure 3. Electrochemical cycling rate performance of chemically delithiated NMC 111 cathodes as compared to the pristine material. The material without binder was mixed with the LiOH·H2O and annealed at 500 °C. The 500 and 925 °C were mixed with 3 wt % PVDF and 5 wt % carbon black before being mixed with LiOH·H2O and heat treated.




The caption:

Figure 4. SEM secondary electron (SE) and EDS elemental imaging of NMC 111 cathode after binder removal with 4 wt % LiOH·H2O.


A heating process to decompose the carbon black and PVDF binder can be an effective methodology for recycling Li-ion battery materials. This process benefits from the addition of a Li source to counteract the tendency of fluorine to pull out Li from the structure. The additional Li can react with the F and Mn from the NMC to form another phase. Additionally, a one-step process can be used to remove binder and relithiate the material; however, this requires higher temperatures than that in the simple binder removal. Although this process does somewhat degrade performance, it should be noted that these studies were utilizing 3 wt % PVDF, and commercial manufacturers typically use substantially less. A reduction in binder amount will lessen the detrimental impacts of binder removal. Overall, this process is a straightforward methodology to remove the PVDF binder and relithiate the cathode material and help enable direct recycling. An efficient direct recycling process has the potential to enable profitable recycling of Li-ion batteries thereby mitigating the effects of their disposal while reducing the costs of Li-ion batteries.


It's not clear that this process will make lithium battery recycling economically viable.

For all my whining about lithium batteries here and in other posts in this space, it should be said that I own a few computers with lithium batteries, so a claim to innocence would not stand scrutiny.

History will not forgive us, nor should it, and to be perfectly clear, I am part of "us."

I trust you're having a pleasant afternoon.

Sources of Water Contributing to Sea Level Rise Since 1900.

The paper I'll discuss in this post is this one: The causes of sea-level rise since 1900 (Frederikse et al., Nature 584, 393–397 (2020))

Most of the time, I incorporate the title of papers I discuss in this space - to the extent possible - in the title of the post, but as it happens, this paper would be better titled as I have done. The main cause of sea level rise is climate change; followed by the removal of fossil ground water for irrigation and ultimately evaporation and transpiration.

The latter cause, the unsustainable mining of fossil ground water for agriculture, as I learned in this lecture a while back, contributes significant amounts of water to the rise in sea level: During the lecture, Dr. Robert Kopp, the speaker, estimated about 10% of sea level rise was attributable to mined ground water, if I recall correctly. Examples of places where fossil ground water is mined in vast amounts are the Ogalalla aquifer underlying significant portions of the American Midwest, and the California aquifer underlying the San Joaquin Valley. Both aquifers are being rapidly depleted and without a source of water, as agricultural zones they will die.

Thinking about all of this has lead me to have elaborate geoengineering fantasies - they are just that, fantasies - involving supercritical water desalination of the surface waters of the very dirty inland sea, the Gulf of Mexico, a process that would involve supercritical water oxidation of microplastics increasingly found there, persistent organic pollutants, oil residues from the far from ameliorated Deepwater Horizon data that went down the memory hole even while the earlier event at Fukushima which in many ways was less odious, didn't, as well as the recovery of carbon dioxide - most of this dumped dangerous fossil fuel waste is in the oceans where it acidifies it, - as well as valuable minerals like calcium, magnesium, uranium, and perhaps copper and zinc, and perhaps most importantly, the phosphorous (and more carbon dioxide) resulting eutrophication generating biomass caused by runoff into the Mississippi from Iowa and neighboring states as part of the so called "renewable energy" disaster represented by ethanol production for motor fuels.

In my fantasy, the water from this process is steam driven to central North America to restore and refill the Ogalalla and other depleted mined waters, Owens Lake, the California aquifer and the dead Colorado River delta. It's a nice fantasy, but it's just that a fantasy. While remotely feasible, I think, it is clear that humanity is far too stupid to embrace such an idea because of the source of energy such a scheme would require. Humanity would rather believe that so called "renewable energy" will save the world. It hasn't saved the world; it isn't saving the world; and it won't save the world, but as we are seeing, to some amazement, the early 21st century is a period in history where the embrace of lies has subsumed and battered the truth.

Happily, truth is not a function of belief, and it will, as it must, because it is truth, reemerge in smarter times.

As for fantasies, sometimes one realizes something like them, but most often not. Meeting someone like my wife was a fantasy I had as a young man, but in many ways she is different, indeed better, than the fantasies. Reality doesn't always suck, but sometimes it does. Acting on fantasies however can also go very badly: Many popular energy fantasies from the last quarter of the 20th century have caused more harm than good. Things are getting worse because of our reliance on the so called "renewable energy" fantasy. Whether reality of draining a little of the ocean by supercritical water desalination would prove to be as good as the fantasy of doing so, will almost certainly never be known.

Anyway...

The paper refines Dr. Kopp's estimation that I remember from Dr. Kopp's wonderful lecture.

I will not see the like again.

(The death of science lectures as a result of Trump's incompetence and lies about Covid-19, is yet another tragedy, perhaps a relatively minor one, among the thousands, that the normalization of his lies and acceptance of his ignorance and corruption has caused. No matter how great a President Joe Biden proves to be; it will be a very long time before we're past this damage, generations probably, caused by this nearly missed triumph of stupidity and racism.)

Anyway...

Anyway...

The abstract, available from the link to the paper above, is worth reading. From the paper's introduction:

Main
Global-mean sea level (GMSL) has increased by approximately 1.5 mm yr^(−1) (refs. 1,4,5) over the twentieth century, modulated by large multidecadal fluctuations6. Changes in GMSL are the net result of many individual geophysical and climatological processes, with some of the largest contributions coming from ice-mass loss and thermal expansion of the ocean. The level of agreement between the sum of these individual contributions and the observed changes in GMSL—often described as the ‘sea-level budget’—is a key indicator of our understanding of the drivers of sea-level rise7. Multiple studies show closure of the sea-level budget within their stated uncertainties since the 1960s and over the era of satellite altimetry since 19938,9,10. However, rates of GMSL change and their contributions to the budget over the entire twentieth century, and especially the first half of the twentieth century, have not yet been fully explained or attributed. Previous observation-based studies concluded that the GMSL budget for the whole twentieth century could not be closed within the estimated uncertainties2,3. Various explanations for this non-closure have been proposed, including an overestimation of the tide-gauge-derived rates of GMSL change11 and underestimation of the ice-sheet contribution12, but there is no agreement yet on the cause of this discrepancy13.

Over the past few years, revised estimates of the main known driving processes of global sea-level rise that cover the entire twentieth century have become available14,15,16,17, the spread among different estimates of twentieth-century glacier mass loss has been reduced18, and improved mapping methods and correction of instrumental bias have resulted in higher estimates of the contribution from thermal expansion since the 1960s19. In parallel, estimates of twentieth-century GMSL change have converged to lower rates than previously estimated, as a result of improved reconstruction approaches, spatial-bias correction schemes, and the inclusion of estimates of local vertical land motion (VLM) at tide-gauge locations4,9,20. As a result of these developments, the GMSL budget needs to be re-estimated, to determine whether the observed sea-level rise since 1900 can be reconciled with the estimated sum of contributing processes...

...To obtain estimates of changes in global ocean mass (barystatic changes), we combine estimates of mass change for glaciers16,21, ice sheets14,22,23,24,25 and terrestrial water storage (TWS). For the TWS estimate, we consider the effects of natural TWS variability17, water impoundment in artificial reservoirs26 and groundwater depletion27,28. For 2003–2018, we use observations from the Gravity Recovery and Climate Experiment (GRACE)29 to quantify the barystatic changes. We estimate changes in sea level due to global thermal expansion (thermosteric changes) from in situ subsurface observations30,31,32 over the period 1957–2018, and combine these estimates with an existing thermosteric reconstruction15. To obtain an estimate of GMSL changes and their accompanying uncertainties, we combine tide-gauge observations with estimates of local VLM from permanent Global Navigation Satellites System (GNSS) stations and with the difference between tide-gauge and satellite-altimetry observations.


The authors note that many traditional methods of measuring sea level, notably tide gauges, are subject to significant variability:

Each tide-gauge and VLM record is affected by glacial isostatic adjustment (GIA) and by the effects of gravity, rotation and deformation (GRD) from contemporary surface-mass redistribution due to changes in ice mass and TWS


VLM here is "vertical land motion" and TWS is "terrestrial water storage" - for example, dams. The authors note that another so called "renewable energy" disaster affecting sea levels - in this case it slowed sea level rise - was the widespread enthusiasm for the construction of these dams, which they state peaked in the 1970's.

Graphics from the text:



The caption:

a, Observed GMSL, and the estimated barystatic and thermosteric contributions and their sum. b, The barystatic contribution and its individual components. The TWS term is the sum of groundwater depletion, water impoundment in artificial reservoirs and the natural TWS term. c, 30-year-average rates of observed GMSL change and of GMSL change as a result of the different contributing processes. d, 30-year-average rates of GMSL change due to the barystatic contribution and its individual components. The shaded regions denote 90% confidence intervals. The values in a and b are relative to the 2002–2018 mean.


GMSL = Global Mean Sea Level. The word barystatic refers to mass transfer, that is ice to seawater, groundwater to seawater, etc. The "static" root of the word is misleading.



The caption:

Figure 2
a, Fraction with all components included. b, Fraction after omitting the TWS component. The shaded regions denote 90% confidence intervals.





The caption:

Figure 3

a–f, Observed basin-mean sea level, and the estimated contributions and their sum, for the different basins (as indicated on the map). Contrary to the global case, GIA causes basin-mean changes in sea level, and so is included in the sum of contributors. The shaded regions denote the 90% confidence interval. The values are relative to the 2002–2018 mean.


There's quite a bit of interesting detail in the discussions of the full paper's text. It's worth reading if one can access it. I do hope to find some time to spend with it.

From the authors' conclusions:

We reconstructed the GMSL since 1900 and compared it to the sum of the contributing processes. We found that these processes explain the observed twentieth-century GMSL trend and match the multidecadal variability pattern, except for the low rates in observed sea-level rise during the 1920s. Barystatic changes are the primary contributor to sea-level rise, with glacier mass loss being the largest component. Reservoir impoundment caused a substantial, albeit temporary, slowdown of GMSL rise during the 1970s. The relative contributions of thermosteric and barystatic changes to GMSL vary with time. On basin scales, trends and multidecadal variability deviate from the global mean, mostly as a result of variability in the steric component...

...Closure of the twentieth-century sea-level budget, as demonstrated here, implies that no additional unknown processes, such as large-scale deep-ocean thermal expansion or additional mass loss from the Antarctic Ice Sheet, are required to explain the observed changes in global sea level. Such additional processes had been speculated to explain the non-closure found in previous studies of global sea-level budget2,3,12. Our demonstration of closure of the global-mean and basin-mean sea-level budget forms a consistent baseline against which process-based and semi-empirical sea-level projections can be benchmarked, without the need to compare against either the sum of processes or observed sea level37. The downward revision of the estimated sea-level rise and updated estimates of the driving processes, particularly the increased estimated glacier mass loss, result in a consistent picture of twentieth-century GMSL rise and its underlying causes.


Cool paper, I think.

I hope you will have as safe and as enjoyable weekend as is possible in these dire times.

For anyone who knows the area, what is Kenosha like, and why do they have a racist police chief?

I'm just curious as to what kind of city and city government would have a cop who thinks it's OK for a cop to shoot an unarmed black man seven times in the back while letting a white kid who openly shot and killed people walk?

Is the town generally racist?

Wired on Waste: Leaving Behind Toxic Trash

I generally don't read the popular press on issues but this news item from the pop website came to me in one of my science news feeds.

It's rare to hear reality on energy anymore, and the atmosphere, as well the land and the sea reflect that.

In fact, the subtitle of the article from Wired below has a stupid oxymoronic statement about a "boon for clean energy."

An intractable waste problem on a scale of millions of tons of solid toxic waste is a "boon for clean energy?"

You can't get a degree in journalism if you've passed a college level science course.

There are many, many, many scientific publications on recycling electronic waste, by the way, and frankly, having read oodles of them, it's not pretty, and by the way, almost all of the processes depend on the use of dangerous fossil fuel derived reagents, highly corrosive reagents, and of course, being "distributed" transport by dangerous fossil fuel powered vehicles to effect.

The sad thing is that this situation exists for a hyped form of energy that has never been, is not now, and never will be a significant form of energy; it always has been, always is and always will be trivial.

Another way our fantasies have screwed all future generations:

Solar Panels Are Starting to Die, Leaving Behind Toxic Trash

By 2050, the International Renewable Energy Agency projects that up to 78 million metric tons of solar panels will have reached the end of their life, and that the world will be generating about 6 million metric tons of new solar e-waste annually. While the latter number is a small fraction of the total e-waste humanity produces each year, standard electronics recycling methods don’t cut it for solar panels. Recovering the most valuable materials from one, including silver and silicon, requires bespoke recycling solutions. And if we fail to develop those solutions along with policies that support their widespread adoption, we already know what will happen.

“If we don’t mandate recycling, many of the modules will go to landfill,” said Arizona State University solar researcher Meng Tao, who recently authored a review paper on recycling silicon solar panels, which comprise 95 percent of the solar market.


By contrast to 78 million tons of solar electronic distributed waste, so called "nuclear waste" having supplied roughly 20% of all American Energy going back to the 1980's, and including all so called "waste" generated by commercial nuclear power since the industry was founded in the late 1950's, amounts to about 80,000 metric tons, in a few highly concentrated locations.

Neither of these figures compare to the hundreds upon hundreds of billions of tons of dangerous fossil fuel waste that have accumulated in the air, as well as on the land and in the sea, while we all waited like Godot for the grand renewable energy nirvana that did not come, is not here, and will not come.

Combined, worldwide, all of the solar and wind facilities on the entire planet have never, not once, produced the 28 exajoules of energy that nuclear energy has routinely provided every damned year since 1990, preventing the release of more than 30 billion tons of dangerous fossil fuel waste, this while being vilified as "dangerous" by a population of people who have never, not once, given a shit about the six to seven million people who die each year from dangerous fossil fuel and "renewable" biomass combustion waste each year, aka, air pollution.

Global, regional, and national comparative risk assessment of 79 behavioural, environmental and occupational, and metabolic risks or clusters of risks, 1990–2015: a systematic analysis for the Global Burden of Disease Study 2015 (Lancet 2016; 388: 1659–724) One can easily locate in this open sourced document compiled by an international consortium of medical and scientific professionals how many people die from causes related to air pollution, particulates, ozone, etc.

Prevented Mortality and Greenhouse Gas Emissions from Historical and Projected Nuclear Power (Pushker A. Kharecha* and James E. Hansen Environ. Sci. Technol., 2013, 47 (9), pp 4889–4895)

If you think the solar and wind industries will solve the energy waste problem, a suggested reading for you: The Myth of Sisyphus.

Have a nice evening.

Lincoln Project: Dear Daughters.

I'm surprised I don't see this one posted here - unless I missed it - but damn, these guys are good:

Synergies of the Zr/Sm Co-doped Fe2O3/CeO2 Oxygen Carrier for Chemical Looping H2 generation.

The paper I'll discuss in this post is this one: Synergistic Effects of the Zr and Sm Co-doped Fe2O3/CeO2 Oxygen Carrier for Chemical Looping Hydrogen Generation (Xiang et al, Energy and Fuels, 2020, 34, 8, 10256–10267.)

Much of what we hear about energy is delusional. Many people, for instance, believe that so called "renewable energy" is having an effect, or will have an effect "by 'such and such' year" on climate change. This has clearly proved to be nonsense, despite nearly half a century of wild cheering and the expenditure of trillions of dollars for no meaningful result other than an increase in the strength of hurricanes. (The fool Mark Z. Jacobson, of Stanford University has published a deliciously amusing paper claiming that wind turbines can stop hurricanes, which begs the question of whether wind turbines can stop, um, the wind: Taming hurricanes with arrays of offshore wind turbines. (Jacobson et al., Nature Climate Change, volume 4, pages 195–200 (2014))

You hear these sort of things, and you don't believe you're hearing correctly, but one needs to be careful in criticizing Dr. Jacobson, since he's rather Trumpian in the sense that he responds to criticism with lawsuits.

Nevertheless he, is, however, which I say at the risk of a lawsuit, delusional. Wind turbines at sea will do little more than further distribute polymers in seawater when these short-lived pieces of shit transform into greasy landfill or even worse, debris on the seafloor.

Another delusional claim that shows up quite a bit is that hydrogen is a clean fuel. This is nonsense. Barring the development of fusion reactors, hydrogen, as the paper I will discuss correctly notes, is an energy carrier, not a form of primary energy, that is, all of the hydrogen on earth is a form of chemically stored energy. As such, making hydrogen wastes energy, and the question of whether it is sustainable to so waste energy depends on the cleanliness of the form of energy itself. A great deal has been written about hydrogen from wind energy in this century and, in fact, before this century. Since wind power is not a clean and sustainable form of energy, hydrogen from wind is not clean and sustainable. Of course, neither is the main source of almost all the hydrogen manufactured on earth clean and sustainable. Currently 95+% of all hydrogen produced industrially comes from dangerous natural gas. Small amounts are generated as a side product of the chlorine industry, but in general, such production has remained trivial for nearly a century.

In my oft stated opinion - and I fully understand that nobody cares what I think - nuclear energy is the only sustainable form of energy there is. In order to advance the technical feasibility of using nuclear energy to address climate change in such a way as to actually remove the dangerous fossil fuel waste accumulated, hydrogen will be required, as a captive intermediate for fixing and sequestering carbon dioxide in the form of useful products, the only economical and sustainable way carbon can be sequestered, via "CCU," carbon capture and utilization.

Nobody cares what I think, or as Rutger Hauer put it:

I've seen things you people wouldn't believe... All those moments will be lost in time, like tears in rain.


Tears in the rain...there is a world worth saving and I cannot stop myself from saying so, though saving it looks more and more difficult because of the human capacity for self delusion.

"Chemical looping" is a process whereby oxygen is delivered to a combustible material when chemically bound to another substance, and - often in direct contact with the combustible material - causes the material to combust with the release of energy. It is not too much of a stretch to consider hemoglobin in blood operating as a chemical looping process, and interestingly blood, like many proposed approaches to chemical looping, utilizes iron as the carrier, since heamglobin is an iron porphyrin complex at its core.

Industrially, chemical looping is designed to oxidize carbon based fuels in such a way that the exhaust is effectively pure carbon dioxide. If the carbon based fuel is biomass derived, this represents a strategy for direct capture of carbon dioxide from the air.

What caught my eye here is the use of cerium, an element that has been proposed for use in the thermochemical splitting of carbon dioxide into its monoxide and oxygen. (Carbon monoxide is a hydrogen equivalent, via the "water gas" reaction.)

From the paper's introduction:

Hydrogen is not only an ideal energy carrier but also an important industrial raw material widely used in chemical engineering, metallurgy, aerospace industry, etc. At present, hydrogen mostly originated from the reforming of fossil fuels, which would be a complex process and bring about abundant emission of CO2 into the atmosphere.
Chemical looping hydrogen generation (CLHG) is a promising technology, which can generate hydrogen of high purity with inherent CO2 capture.(1,2) It was composed of three consecutively connected reactors, i.e., fuel reactor (FR), steam reactor (SR), and air reactor (AR), and Fe2O3 is the most promising oxygen carrier for CLHG.(3,4) The fuel is oxidized into H2O and CO2 in the FR with Fe2O3 reduction into FeO or Fe; then FeO/Fe is oxidized into Fe3O4 in the SR with hydrogen generated; and Fe3O4 is transferred into the AR with Fe2O3 regenerated.

A support is necessary to improve the redox stability of the Fe-based oxygen carrier, and CeO2, as a typical fluorite oxide, is an active support, which can boost the reactivity and eliminate the carbon deposition of the oxygen carrier through promoting the lattice oxygen conductivity.(5,6) The lattice oxygen conductivity is critical for the redox reactivity and sintering resistance of the Fe-based oxygen carrier.(7−10) Specifically, doping CeO2 with cations with a smaller radius or lower valence can further increase the oxygen mobility because the cations with a smaller radius could decrease the oxygen vacancy formation energy(11,12) and the cations with a lower valence could give rise to more oxygen vacancies for charge neutrality.(13,14)
Zr4+, with a smaller radius (0.084 nm) than Ce4+ (0.097 nm), is the best known and most usually investigated doping cation for CeO2.(13) The insertion of Zr4+ could cause the contraction distortion of the CeO2 crystal cell, reducing the strain to accommodate the larger Ce3+ (0.107 nm), such that oxygen vacancies can be easily generated around the Zr4+ cations, leading to high oxygen mobility.(12,15) Moreover, ZrO2 is a desirable inert support for the chemical looping process with high thermal and chemical stabilities. The CeO2-based solid solution originating from ZrO2 modification always shows high thermal stability and promotes oxygen storage capacity in heterogeneous catalysis, such as three-way catalyst (TWC), catalytic oxidation of CH4, and volatile organic compounds (VOCs).(16−19)


Since the oxidizing reaction involves the use of steam to generate hydrogen, this system is effectively a thermochemical water spitting procedure.

There has been much discussion in the literature on the subject of oxygen permeable transport materials, one class of such materials being perovskites. Perovskites also discussed widely in connection with the useless solar industry, and usually the perovskites in question are lead based; you can have a delicious conversation with stupid people about whether distributing lead for distributed energy is a good idea; I had a wonderful conversation along these lines with a dumb person over in the benighted E&E forum, where one can learn that so called "renewable energy" is saving the world and at the same time learn that climate change is getting worse and worse.

You hear these sort of things, and you don't believe you're hearing correctly...

Several years back I spent a lot of time studying papers on the subject of oxygen transporting perovskites, compiling a spreadsheet of all papers published over a period of time with columns for each element utilized in them to allow for sorting them. From my notes, it seems I abandoned this task around 2015, when I realized that most of these transport perovskites were unstable in the presence of carbon dioxide. Perhaps this paper, as a chemical looping procedure, avoids this problem. I just opened one of those old spreadsheets, and I note the presence therein of a number of papers over the period I was searching involving the elements in this system, notably iron, cerium and samarium.

The authors of this paper offer a note about the use of samarium:

For doping cations in CeO2 with lower valence, rare earth cations with 3+ valence are the most widely used cations.(13) In addition to the promoted oxygen conductivity, it has been found that the rare earth doping could also improve the stability of CeO2. La-doped CeO2 could maintain high lattice oxygen conductivity even after calcination at 1000 °C(28) and shows higher oxygen storage capacity and catalytic oxidation ability than CeO2–ZrO2 mixed oxides.(29) He et al.(30) claimed that CeO2 with Y doping could induce abundant lattice defects and active sites for catalytic decomposition of CH3SH. The oxygen mobility of CeO2-based solid solution is closely related to the species of rare earth elements.(13,31) Sm- and Gd-doped CeO2 have been recognized as the highest oxygen-conductive solid solutions among the rare-earth-doped CeO2.(32−34) Furthermore, the oxygen mobility in CeO2 with Sm dopant is higher than that with Gd as a result of its more oxygen vacancy defects,(35−39) although some controversial findings suggested that Gd-doped CeO2 was superior to that of Sm.(40) Specifically, Anjaneya et al.(41) observed the highest ionic conductivity as well as the lowest activation energy in Ce0.8Sm0.2O1.9, and Yahiro et al.(32) found that the oxygen conductivity of Ce0.8Sm0.2O1.9 was about twice that of Ce0.8Gd0.2O1.9. Given the excellent properties of rare-earth-doped CeO2, they have been applied in the catalytic oxidation of soot, CH4, CO, and VOCs.(14,42−45)

It is worthy to mention that the CeO2–rare earth mixed oxides have also been applied in chemical looping processes. Hedayati et al.(46) indicated that Ce0.9Gd0.1O1.9 could enhance the reactivity and showed satisfactory fluidization, sintering, and agglomeration resistance as a support for CuO, Fe2O3, and Mn2O3 in chemical looping combustion (CLC). Besides, Kosaka et al.(47) reported that Gd-doped CeO2 could promote the reduction of Fe2O3, especially for the deep reduction from FeO to Fe, because Gd-doped CeO2 could enhance the outward mobility of lattice oxygen in the particles. Zeng et al...

...Our group compared rare earth elements, Y, La, and Sm, doped CeO2 as the supports for the Fe-based oxygen carrier in CLHG,(50) finding that Fe2O3/Ce0.8Sm0.2O1.9 was the most active oxygen carrier and had the highest oxygen vacancy concentration; however, the Fe-based oxygen carrier with rare-earth-doped CeO2 as a support exhibited low sintering resistance, exerting a detrimental effect on the reactivity. Considering the excellent thermal stability of ZrO2,(51,52) Zr-doped CeO2 could not only improve the store/release oxygen properties but also promote the thermal stability of the oxygen carrier.(27) Therefore, it could be anticipated that the co-doping of rare earth and Zr into CeO2 as a support for Fe2O3 could bring about desirable performance for CLHG.


The fuel utilized in the "fuel" reactor, is in fact, carbon monoxide in this paper. Because of ash considerations - a consideration in any chemical looping procedure - it is necessary to use relatively pure, or at least ash free fuels in these systems. This is an important caveat, although one can imagine systems for addressing this concern.

Some pictures from the text:



The caption:

Figure 1. (a) XRD patterns of fresh oxygen carriers. (b) Enlarged view for the (111) reflection of CeO2. (c) Enlarged view for the (110) reflection of Fe2O3.




The caption:
Figure 2. H2-TPR patterns of prepared oxygen carriers.


"TPR" here is a technique known as "temperature programmed (hydrogen) reduction" which was utilized to characterize the oxygen carrier. The instrument model is BELCAT-B (MicrotracBEL Japan, Inc.), which is a surface area measuring instrument similar to those for "BET" (Brunauer–Emmett–Teller) surface area measurements.

The hydrogen production reactivity seems to be fairly stable through a number of cycles:



The caption:

Figure 3. Effect of the redox cycle on the H2 yield for various oxygen carriers.


In this paper, nitrogen was utilized as a carrier gas, and thus the system did not produce pure carbon dioxide. This is an issue that would need to be addressed in any attempt to pilot and especially commercialize this sort of system.



The caption:

Figure 4. CO2 concentration in the reduction stage of the 10th cycle.




The caption:

Figure 5. Conversion rates of oxygen carriers in the reduction stage of the 10th cycle.


"Roc" refers to the conversion rate.



The caption:

Figure 6. XRD patterns of oxygen carriers before and after cycles.

The morphology of these material has clearly changed after cycling, but does not seem to have had a huge effect on function. Whether this would be the case for thousands of cycles, as well might be required for any industrial system using this technology, is an open question.



The caption:

Figure 7. SEM images of oxygen carriers before and after redox cycles.




The caption:

Figure 8. EDX analysis of oxygen carriers before and after cycles.


"EDX" is a technique known as "energy dispersive x-ray analysis"



The caption:

Figure 9. XPS O 1s spectra of the oxygen carriers after cycles.


"XPS" is x-ray photoelectron spectroscopy, which measures the energy levels of electrons in the material, giving information about its structure. In this context, it is utilized to measure oxygen vacancies which are necessary for oxygen to migrate in the material.

An excerpt of the conclusion:

...Fe2O3/Ce0.6Sm0.15Zr0.25O1.925 was the best considering the reactivity, redox stability, H2 yield and purity. The reactivity of samples followed the sequence Fe2O3/Ce0.6Sm0.15Zr0.25O1.925 > Fe2O3/Ce0.8Sm0.2O1.9 > Fe2O3/Ce0.75Zr0.25O2 > Fe2O3/CeO2. The Sm dopant was mainly inserted into CeO2, and a small amount of it was doped into Fe2O3. Nevertheless, the Zr dopant could only be doped into CeO2. The Zr and Sm doping could restrain the growth of the CeO2 and Fe2O3 crystallites and alleviate the sintering of the oxygen carrier. Moreover, the Zr and Sm doping could enhance the oxygen mobility of the oxygen carrier and improve the consistency of the reduction extent in the whole particle, and the concentration of oxygen vacancy was ranked as Fe2O3/Ce0.8Sm0.2O1.9 > Fe2O3/Ce0.6Sm0.15Zr0.25O1.925 > Fe2O3/Ce0.75Zr0.25O2 > Fe2O3/CeO2. Both Zr and Sm doping could restrain the outward diffusion of Fe cations to the particle surface, improving the sintering resistance and the redox stability of the oxygen carrier, and the co-doped sample Fe2O3/Ce0.6Sm0.15Zr0.25O1.925 achieved the best performance. Serious sintering occurred for cycled Fe2O3/CeO2, and the Zr doping could enhance the sintering resistance significantly and, thus, improve the reactivity. Nevertheless, the Sm doping promoted the reactivity of Fe2O3/CeO2 mainly by increasing the oxygen mobility, and its improvement effect on thermal stability was quite limited. In addition, both Zr and Sm could be incorporated into CeO2 for prepared Fe2O3/Ce0.6Sm0.15Zr0.25O1.925...


Like tears in the wind...

Little papers like this offer me some hope for a future, smarter generation, in the future.

...tears in the wind...

Wind turbines will not stop hurricanes, because they will not stop climate change.

It's funny this morning, because I often think of nuclear power plants along the coast of the Gulf of Mexico, because I dream of things like refilling the Ogallala aquifer, Lake Owens, the California groundwater aquifers as a path to draining the oceans, while simultaneously cleaning the filth laden Gulf of its oil residues, it's micro and macro plastics, the explosive growth of eutrophication plants, this while recovering precious phosphorous.

These are big dreams, giant dreams, beyond anything of which I am capable, "like tears in the rain." But as I approach the end of my life, these possibilities, the existence of which I have convinced myself, as possibilities as opposed to certainties fill me with blind hope for a future of which future generations may have been robbed.

I can only imagine the paroxysms of stupid concern that the existence of a chain of nuclear power plants powering such a clean up in the Galveston, Lake Charles area might have inspired this morning. Certainly they would drown out any whimpers of concern about the dangerous fossil fuel infrastructure in that area, which is both real, and a far higher risk than anything associated with the big bogeyman at, say Fukushima.

Nuclear power plants wouldn't stop the wind but the could arrest climate change, but could is a conditional word, except in the imagination in which people at Greenpeace, for instance, say list all the things that so called "renewable energy" could do, as if "could" was the same as "is" but, in fact, so called "renewable energy hasn't done, isn't doing, and frankly won't do anything to address climate change.

The climate is shuffling off the weight of humanity. Ironically, the science of thermodynamics, high temperatures in already hot times are required.

This lovely little paper, obscure as the contents may be to the general public, demonstrates how this might be.

I trust you are safe and well in these very challenging, and frankly, frightful times.





Eleanor Rigby.

Another Casualty of Trumpism: The Credibility of the FDA.

There have been some actions of the FDA with which I have disagreed, but overall, the FDA is a critical, absolutely critical regulatory agency, driven by high scientific integrity, for the maintenance of safe medications.

The FDA saves lives, and all around the world, until now, regulatory agencies all around the world have aspired to meeting its example of integrity, standards, and guidance.

Well, the orange racist unintelligent corrupt thug as greatly damaged the reputation of this important American infrastructure:

From Fierce Pharma:

Critics are slamming the FDA and Commissioner Stephen Hahn for authorizing COVID-19 plasma treatment prematurely, but the issue is much broader than one emergency use authorization. The agency's reputation is on the line. And if it falls, the pharma industry will pay a hefty price.

Since Hahn stood beside President Trump Sunday to announce the plasma authorization, critics of all kinds have lit up social media—commenting that they can’t trust the FDA, or won’t take drugs it approves or, perhaps most notably, won’t get a COVID-19 vaccine even if stamped with the agency's approval.

And there's some basis for the concerns that FDA decisionmaking has been politicized. Recently, the White House strategized about pushing AstraZeneca's vaccine to market before the election, ahead of full data from its 30,000-patient late-stage trial, according to reports. President Trump himself has repeatedly promised to have a vaccine by October. Indeed, in a controversial tweet that helped spark the plasma controversy, the president accused the agency of being part of a "deep state" effort to slow-walk vaccines until the election.

While AstraZeneca refuted reports of a fast track for its shot, telling FiercePharma it has not discussed any emergency authorization with the U.S. government, the constant swirl of rumors around vaccine approval, along with the FDA's most recent actions, have experts worried about the effects on the agency's independence and public confidence in its decisions, particularly during the pandemic.

“FDA's credibility has never been more important and more threatened simultaneously,” said Mark Senak, a public relations professional and Eye on FDA blogger, especially as phase 3 data on COVID-19 drugs and vaccines begin to come in and the need for public trust increases.

RELATED: FDA's emergency nod for convalescent plasma sparks questions of whether it's bowing to Trump

Senak has written about the problem of a politicized FDA since December, saying Monday that “if there were concerns then, it is only compounded now in the midst of a pandemic.”

Some press releases from the FDA, for instance, have made the FDA sound like cheerleaders for the Trump administration, Senak said, including the plasma release which is absolutely “cheerleader language.” The title? “FDA Issues Emergency Use Authorization for Convalescent Plasma as Potential Promising COVID–19 Treatment, Another Achievement in Administration’s Fight Against Pandemic.”

Data from The Harris Poll, which has tracked public sentiment around the coronavirus since March, shows that among trusted resources for COVID-19 information, 78% of American say scientists are trustworthy, while only 49% say the same of the White House and president.



FDA faces a reputation crisis amid Trump pressure for fast COVID action—and that's bad news for pharma

This stupid evil man doesn't care what or who he kills to satisfy his childish ego.
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