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Record W4391611355 · doi:10.1002/cphc.202300889

Understanding the Mechanism of Urea Oxidation from First‐Principles Calculations

2024· article· en· W4391611355 on OpenAlexafffund
Stephen W. Tatarchuk, Rachelle M. Choueiri, Alexander MacKay, Shayne Johnston, William Cooper, Kayla S. Snyder, Jury J. Medvedev, Anna Klinkova, Leanne D. Chen

Bibliographic record

VenueChemPhysChem · 2024
Typearticle
Languageen
FieldMaterials Science
TopicCatalytic Processes in Materials Science
Canadian institutionsUniversity of WaterlooUniversity of Guelph
FundersNatural Sciences and Engineering Research Council of Canada
KeywordsMechanism (biology)ChemistryUreaComputational chemistryReaction mechanismChemical physicsCatalysisOrganic chemistryPhysicsQuantum mechanics

Abstract

fetched live from OpenAlex

Abstract Developing electrocatalysts for urea oxidation reaction (UOR) works toward sustainably treating urea‐enriched water. Without a clear understanding of how UOR products form, advancing catalyst performance is currently hindered. This work examines the thermodynamics of UOR pathways to produce N 2 , NO 2 − , and NO 3 − on a (0001) β ‐Ni(OH) 2 surface using density functional theory with the computational hydrogen electrode model. Our calculations show support for two major experimental observations: (1) N 2 favours an intramolecular mechanism, and (2) NO 2 − /NO 3 − are formed in a 1 : 1 ratio with OCN − . In addition, we found that selectivity between N 2 and NO 2 − /NO 3 − on our model surface appears to be controlled by two key factors, the atom that binds the surface intermediates to the surface and how they are deprotonated. These UOR pathways were also examined with a Cu dopant, revealing that an experimentally observed increased N 2 selectivity may originate from increasing the limiting potential required to form NO 2 − . This work builds towards developing a more complete atomic understanding of UOR at the surface of NiO x H y electrocatalysts.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

How this classification was reachedexpand

Full frame distilled prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.178
Threshold uncertainty score0.745

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0010.000

Machine scores (provisional)

The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.

Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.

Opus teacher head0.091
GPT teacher head0.279
Teacher spread0.188 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one teacher head, not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designBench or experimental
Domainnot available
GenreEmpirical

How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".

Quick stats

Citations19
Published2024
Admission routes2
Has abstractyes

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