An honorable retraction of a highly cited paper on renewable energy based ammonia synthesis.

[NNadir]

When I opened up the issue of Science this morning, I came across this rather - in my opinion - honorable retraction of a six year old paper on the production of ammonia using so called "renewable energy." (Ammonia, the synthesis is critical to the world food supply, is overwhelmingly synthesized using dangerous natural gas, followed by coal, as an energy source.)

The retraction is here: Retraction Stuart Licht1,*, Baochen Cui1, Baohui Wang1, Fang-Fang Li1, Jason Lau2, Shuzhi Liu1 (Science, Vol. 369, Issue 6505, pp. 780 14 Aug 2020)

Many, most, retractions involve some level of fraud, but I don't think this is the case here; the paper may represent an honest mistake, although it does appear that the origins of the mistake were uncovered in other labs.

The full (brief) retraction text:

We have obtained new evidence, 6 years after the publication of our Report “Ammonia synthesis by N2 and steam electrolysis in molten hydroxide suspensions of nanoscale Fe2O3” (1), that there is a trace NOx? impurity in the nanoscale Fe2O3 that was unknown at the time. We no longer have the original nanoscale Fe2O3, and manufacturers' content levels of impurities in chemicals may vary over time. However, recently purchased nanoscale Fe2O3 per gram contains 0.0005 g N as NOx?, and an 15N2 isotopic tracer analysis conducted by Wenzhen Li, Yifu Chen, and Hengzhou Liu at Iowa State University; Shuang Gu at Wichita State University; and author S.L. suggests that this trace impurity, rather than N2, is the major nitrogen reactant in the observed ammonia synthesis. We are retracting the original Report, and we encourage exploration of an N2 to NOx? intermediate to ammonia pathway, rather than direct elemental nitrogen pathway, to ammonia synthesis. All observed stimulation of ammonia generation with these (likely NOx?-containing) nanoscale Fe2O3 materials, as well as all thermodynamic calculation results, remain accurate as documented in the original Report.

I have not looked into this paper to any extent, but apparently, according to Retraction Watch, it was highly cited, being in one of the most prestigious journals in the world:

Authors retract highly cited 2014 Science paper

The authors of a 2014 paper in Science have retracted it, after becoming aware that impurities in the chemicals they used for their experiments may have generated the apparent findings.

The paper, “Ammonia synthesis by N2 and steam electrolysis in molten hydroxide suspensions of nanoscale Fe2O3,” has been cited 323 times, according to Clarivate Analytics’ Web of Science, earning it a “hot paper” designation. According to a summary of the work, “the protocol points to a way to produce ammonia from purely renewable resources.”

[eppur_se_muova]

1. Thanks. N2 fixation is something I've always kept in the back of my mind.

(Me, and every other chemist wanting to make an easy $billion.)

[NNadir]

2. A great deal has been written on electrochemical fixation in recent years.

One hopes it will all pan out.

The next problem, of course, is dealing with the N2O that results from the production of ammonia. This is a very, very, very serious environmental issue.

[CatLady78]

3. Missed that

Huh..did not notice that one. I scan retraction watch daily as I am on the mailing list but did not see this.

[NNadir]

4. I'm not sure it was covered in "Retraction Watch." It was in Science. n/t.

[CatLady78]

5. Got it-Thanks.nt

[NNadir]

6. I'm not sure these sordid cases will show up in "Retraction Watch."

Retraction of “Synthesis of Optically Active ZnS–Carbon Nanotube Nanocomposites in Supercritical Carbon Dioxide via a Single Source Diethyldithiocarbamate Precursor”

The authors retract this Article (DOI: 10.1021/ie301553g) following the voluntary admission of Michael J. Casciato that this Article contained data that he had fabricated.

The scanning electron microscope (SEM) and transmission electron microscope (TEM) data in this paper were legitimate; however, the histogram data for particle size were falsified. The XRD results and Table 1 contain data that were falsified and fabricated, and the falsified XRD data were used in the particle size calculation described in the text. The UV/vis and photoluminescence data were fabricated, along with data derived from these figures. As such, the Article is being retracted.

The original Article was published on August 14, 2012 and retracted on August 7, 2020.

Retraction of “Initial Experimental Design Methodology Incorporating Expert Conjecture, Prior Data, and Engineering Models for Deposition of Iridium Nanoparticles in Supercritical Carbon Dioxide”

The authors retract this Article (DOI: 10.1021/ie400996g) following the voluntary admission of Michael J. Casciato that this article contained data that he had fabricated.

Synthesis experiments were conducted and some of the nanoparticle size data were estimated based on photos of nanoparticles on the substrates. Other nanoparticle size data were falsified or fabricated. The modeling approaches, algorithms, and model outputs described are valid and were implemented, but they were applied to these data that were improperly manipulated. The data related to expert opinion were collected and are legitimate. However, based on the falsified and fabricated portion of the work, the article is being retracted.

The original Article was published on June 19, 2013 and retracted on August 7, 2020.

Some years back, I had a pretty intense interest in supercritical carbon dioxide, particularly during the 2008 acetonitrile shortage.

I've recently thought about it in connection with the Allam cycle.

I can't say I was familiar with these papers though.

Pretty nasty stuff. It appears that Casciato now works for an oil company, Shell.