Single-Atom Catalysts for CO<sub>2</sub> Reduction to Oxalate: Theoretical Design and Reaction Condition Prediction

The electrochemical conversion of carbon dioxide (CO<sub>2</sub>) into high-value-added products under mild conditions is crucial for achieving carbon neutrality. Oxalate (C<sub>2</sub>O<sub>4</sub><sup>2–</sup>) is one of the most important industrial...

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محفوظ في:
التفاصيل البيبلوغرافية
المؤلف الرئيسي: Ying Zhou (25031) (author)
مؤلفون آخرون: Xuan Wu (126953) (author), Ping Zhu (11521) (author), Wenhua Zhang (317886) (author)
منشور في: 2025
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author Ying Zhou (25031)
author2 Xuan Wu (126953)
Ping Zhu (11521)
Wenhua Zhang (317886)
author2_role author
author
author
author_facet Ying Zhou (25031)
Xuan Wu (126953)
Ping Zhu (11521)
Wenhua Zhang (317886)
author_role author
dc.creator.none.fl_str_mv Ying Zhou (25031)
Xuan Wu (126953)
Ping Zhu (11521)
Wenhua Zhang (317886)
dc.date.none.fl_str_mv 2025-08-23T03:16:23Z
dc.identifier.none.fl_str_mv 10.1021/acsami.5c11771.s011
dc.relation.none.fl_str_mv https://figshare.com/articles/dataset/Single-Atom_Catalysts_for_CO_sub_2_sub_Reduction_to_Oxalate_Theoretical_Design_and_Reaction_Condition_Prediction/29972284
dc.rights.none.fl_str_mv CC BY-NC 4.0
info:eu-repo/semantics/openAccess
dc.subject.none.fl_str_mv Science Policy
Environmental Sciences not elsewhere classified
Biological Sciences not elsewhere classified
Chemical Sciences not elsewhere classified
reaction condition prediction
2 –</ sup
varying reaction conditions
offers theoretical guidance
achieving carbon neutrality
ti – n
cr – n
single metal atoms
alongside high selectivity
2 </ sub
c – c
– n
x </
theoretical design
mild conditions
carbon dioxide
widely used
using single
systematically tuning
sub ><
remarkably low
reducing agent
promising catalysts
operating efficiently
mechanistic understanding
highly sensitive
findings demonstrate
energy barrier
electrode potential
determining step
designing high
coordination environment
catalytic performance
catalytic activity
atom catalysts
also deepens
added products
6 v
31 ev
dc.title.none.fl_str_mv Single-Atom Catalysts for CO<sub>2</sub> Reduction to Oxalate: Theoretical Design and Reaction Condition Prediction
dc.type.none.fl_str_mv Dataset
info:eu-repo/semantics/publishedVersion
dataset
description The electrochemical conversion of carbon dioxide (CO<sub>2</sub>) into high-value-added products under mild conditions is crucial for achieving carbon neutrality. Oxalate (C<sub>2</sub>O<sub>4</sub><sup>2–</sup>) is one of the most important industrial raw materials and is widely used as a reducing agent in the fields of medicine, dyeing, and plastics yet faces challenges in efficient C–C bond formation under mild conditions. In this study, we investigate the reduction of CO<sub>2</sub> to C<sub>2</sub>O<sub>4</sub><sup>2–</sup> using single-atom catalysts (SACs) with M–N<sub><i>x</i></sub>–C configurations, employing density functional theory (DFT) to assess their catalytic performance under varying reaction conditions. Our findings demonstrate that the catalytic activity of Ti–N<sub>3</sub>–C is highly sensitive to the choice of solvent and electrode potential. Lower solvent dielectric constants and more negative electrode potentials promote oxalate formation with Ti–N<sub>3</sub>–C, exhibiting a remarkably low-energy barrier (0.31 eV) for the rate-determining step at −0.7 V in acetonitrile, alongside high selectivity. By systematically tuning the coordination environment of single metal atoms, we identify Ti–N<sub>2</sub>C–C, Cr–N<sub>2</sub>C–C, and Cr–N<sub>3</sub>–C as promising catalysts, operating efficiently at potentials of −0.7, −0.7, and −0.6 V, respectively. This work not only offers theoretical guidance for designing high-performance SACs for CO<sub>2</sub> conversion but also deepens the mechanistic understanding of the electrochemical CO<sub>2</sub> reduction pathways.
eu_rights_str_mv openAccess
id Manara_030e552a030d1eddac4e57b3188d623f
identifier_str_mv 10.1021/acsami.5c11771.s011
network_acronym_str Manara
network_name_str ManaraRepo
oai_identifier_str oai:figshare.com:article/29972284
publishDate 2025
repository.mail.fl_str_mv
repository.name.fl_str_mv
repository_id_str
rights_invalid_str_mv CC BY-NC 4.0
spelling Single-Atom Catalysts for CO<sub>2</sub> Reduction to Oxalate: Theoretical Design and Reaction Condition PredictionYing Zhou (25031)Xuan Wu (126953)Ping Zhu (11521)Wenhua Zhang (317886)Science PolicyEnvironmental Sciences not elsewhere classifiedBiological Sciences not elsewhere classifiedChemical Sciences not elsewhere classifiedreaction condition prediction2 –</ supvarying reaction conditionsoffers theoretical guidanceachieving carbon neutralityti – ncr – nsingle metal atomsalongside high selectivity2 </ subc – c– nx </theoretical designmild conditionscarbon dioxidewidely usedusing singlesystematically tuningsub ><remarkably lowreducing agentpromising catalystsoperating efficientlymechanistic understandinghighly sensitivefindings demonstrateenergy barrierelectrode potentialdetermining stepdesigning highcoordination environmentcatalytic performancecatalytic activityatom catalystsalso deepensadded products6 v31 evThe electrochemical conversion of carbon dioxide (CO<sub>2</sub>) into high-value-added products under mild conditions is crucial for achieving carbon neutrality. Oxalate (C<sub>2</sub>O<sub>4</sub><sup>2–</sup>) is one of the most important industrial raw materials and is widely used as a reducing agent in the fields of medicine, dyeing, and plastics yet faces challenges in efficient C–C bond formation under mild conditions. In this study, we investigate the reduction of CO<sub>2</sub> to C<sub>2</sub>O<sub>4</sub><sup>2–</sup> using single-atom catalysts (SACs) with M–N<sub><i>x</i></sub>–C configurations, employing density functional theory (DFT) to assess their catalytic performance under varying reaction conditions. Our findings demonstrate that the catalytic activity of Ti–N<sub>3</sub>–C is highly sensitive to the choice of solvent and electrode potential. Lower solvent dielectric constants and more negative electrode potentials promote oxalate formation with Ti–N<sub>3</sub>–C, exhibiting a remarkably low-energy barrier (0.31 eV) for the rate-determining step at −0.7 V in acetonitrile, alongside high selectivity. By systematically tuning the coordination environment of single metal atoms, we identify Ti–N<sub>2</sub>C–C, Cr–N<sub>2</sub>C–C, and Cr–N<sub>3</sub>–C as promising catalysts, operating efficiently at potentials of −0.7, −0.7, and −0.6 V, respectively. This work not only offers theoretical guidance for designing high-performance SACs for CO<sub>2</sub> conversion but also deepens the mechanistic understanding of the electrochemical CO<sub>2</sub> reduction pathways.2025-08-23T03:16:23ZDatasetinfo:eu-repo/semantics/publishedVersiondataset10.1021/acsami.5c11771.s011https://figshare.com/articles/dataset/Single-Atom_Catalysts_for_CO_sub_2_sub_Reduction_to_Oxalate_Theoretical_Design_and_Reaction_Condition_Prediction/29972284CC BY-NC 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/299722842025-08-23T03:16:23Z
spellingShingle Single-Atom Catalysts for CO<sub>2</sub> Reduction to Oxalate: Theoretical Design and Reaction Condition Prediction
Ying Zhou (25031)
Science Policy
Environmental Sciences not elsewhere classified
Biological Sciences not elsewhere classified
Chemical Sciences not elsewhere classified
reaction condition prediction
2 –</ sup
varying reaction conditions
offers theoretical guidance
achieving carbon neutrality
ti – n
cr – n
single metal atoms
alongside high selectivity
2 </ sub
c – c
– n
x </
theoretical design
mild conditions
carbon dioxide
widely used
using single
systematically tuning
sub ><
remarkably low
reducing agent
promising catalysts
operating efficiently
mechanistic understanding
highly sensitive
findings demonstrate
energy barrier
electrode potential
determining step
designing high
coordination environment
catalytic performance
catalytic activity
atom catalysts
also deepens
added products
6 v
31 ev
status_str publishedVersion
title Single-Atom Catalysts for CO<sub>2</sub> Reduction to Oxalate: Theoretical Design and Reaction Condition Prediction
title_full Single-Atom Catalysts for CO<sub>2</sub> Reduction to Oxalate: Theoretical Design and Reaction Condition Prediction
title_fullStr Single-Atom Catalysts for CO<sub>2</sub> Reduction to Oxalate: Theoretical Design and Reaction Condition Prediction
title_full_unstemmed Single-Atom Catalysts for CO<sub>2</sub> Reduction to Oxalate: Theoretical Design and Reaction Condition Prediction
title_short Single-Atom Catalysts for CO<sub>2</sub> Reduction to Oxalate: Theoretical Design and Reaction Condition Prediction
title_sort Single-Atom Catalysts for CO<sub>2</sub> Reduction to Oxalate: Theoretical Design and Reaction Condition Prediction
topic Science Policy
Environmental Sciences not elsewhere classified
Biological Sciences not elsewhere classified
Chemical Sciences not elsewhere classified
reaction condition prediction
2 –</ sup
varying reaction conditions
offers theoretical guidance
achieving carbon neutrality
ti – n
cr – n
single metal atoms
alongside high selectivity
2 </ sub
c – c
– n
x </
theoretical design
mild conditions
carbon dioxide
widely used
using single
systematically tuning
sub ><
remarkably low
reducing agent
promising catalysts
operating efficiently
mechanistic understanding
highly sensitive
findings demonstrate
energy barrier
electrode potential
determining step
designing high
coordination environment
catalytic performance
catalytic activity
atom catalysts
also deepens
added products
6 v
31 ev