Engineering Ag-Nx Single-Atom Sites on Porous Concave N-Doped Carbon for Boosting CO2 Electroreduction.

The electrochemical CO2 reduction reaction (CO2RR) offers an environmentally benign pathway for renewable energy conversion and further regulation of the environmental CO2 concentration to achieve carbon cycling. However, developing desired electrocatalysts with high CO Faradaic efficiency (FECO) at an ultralow overpotential remains a grand challenge. Herein, we report an effective CO2RR electrocatalyst that features Ag single-atom coordinated with three nitrogen atoms (Ag1-N3) anchored on porous concave N-doped carbon (Ag1-N3/PCNC), which is identified by X-ray absorption spectroscopy. Ag1-N3/PCNC shows a low CO2RR onset potential of -0.24 V, high maximum FECO of 95% at -0.37 V, and high CO partial current density of 7.6 mA cm-2 at -0.55 V, exceeding most of the previous Ag electrocatalysts. The in situ infrared absorption spectra technique proves that Ag1-N3 single-atom sites have sole linear-adsorbed CO and can easily desorb *CO species to achieve the highest CO selectivity in comparison with the corresponding counterparts. This work provides significant inspiration on boosting CO2RR by tuning the active center at an atomic level to achieve a specific absorption with an intermediate.

[1]  U. Diebold,et al.  Unraveling CO adsorption on model single-atom catalysts , 2021, Science.

[2]  Wilson A. Smith,et al.  In Situ ATR-SEIRAS of Carbon Dioxide Reduction at a Plasmonic Silver Cathode. , 2020, Journal of the American Chemical Society.

[3]  Jyhfu Lee,et al.  Controlling the Oxidation State of Cu Electrode and Reaction Intermediates for Electrochemical CO2 Reduction to Ethylene. , 2020, Journal of the American Chemical Society.

[4]  Z. Bao,et al.  Understanding the Origin of Highly Selective CO2 Electroreduction to CO on Ni, N-doped Carbon Catalysts. , 2020, Angewandte Chemie.

[5]  Yadong Li,et al.  Tuning the coordination environment in single-atom catalysts to achieve highly efficient oxygen reduction reactions. , 2019, Journal of the American Chemical Society.

[6]  Qinghua Zhang,et al.  A universal ligand mediated method for large scale synthesis of transition metal single atom catalysts , 2019, Nature Communications.

[7]  Tao Zhang,et al.  Unraveling the coordination structure-performance relationship in Pt1/Fe2O3 single-atom catalyst , 2019, Nature Communications.

[8]  Jingguang G. Chen,et al.  Tuning the activity and selectivity of electroreduction of CO2 to synthesis gas using bimetallic catalysts , 2019, Nature Communications.

[9]  Michael B. Ross,et al.  Designing materials for electrochemical carbon dioxide recycling , 2019, Nature Catalysis.

[10]  Xueping Qin,et al.  Active Sites on Heterogeneous Single-Iron-Atom Electrocatalysts in CO2 Reduction Reaction , 2019, ACS Energy Letters.

[11]  Hao Ming Chen,et al.  Atomically dispersed Fe3+ sites catalyze efficient CO2 electroreduction to CO , 2019, Science.

[12]  T. Jaramillo,et al.  Influence of Atomic Surface Structure on the Activity of Ag for the Electrochemical Reduction of CO2 to CO , 2019, ACS Catalysis.

[13]  Lirong Zheng,et al.  Fe–N–C electrocatalyst with dense active sites and efficient mass transport for high-performance proton exchange membrane fuel cells , 2019, Nature Catalysis.

[14]  Genevieve Saur,et al.  What Should We Make with CO2 and How Can We Make It , 2018 .

[15]  Wilson A. Smith,et al.  In Situ Fabrication and Reactivation of Highly Selective and Stable Ag Catalysts for Electrochemical CO2 Conversion , 2018, ACS energy letters.

[16]  Yadong Li,et al.  Design of Single-Atom Co-N5 Catalytic Site: A Robust Electrocatalyst for CO2 Reduction with Nearly 100% CO Selectivity and Remarkable Stability. , 2018, Journal of the American Chemical Society.

[17]  S. Jiang,et al.  Atomically Dispersed Transition Metals on Carbon Nanotubes with Ultrahigh Loading for Selective Electrochemical Carbon Dioxide Reduction , 2018, Advanced materials.

[18]  Christopher J. Chang,et al.  Reticular Electronic Tuning of Porphyrin Active Sites in Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction. , 2018, Journal of the American Chemical Society.

[19]  Yi Cui,et al.  Transition-Metal Single Atoms in a Graphene Shell as Active Centers for Highly Efficient Artificial Photosynthesis , 2017 .

[20]  W. Chu,et al.  Exclusive Ni-N4 Sites Realize Near-Unity CO Selectivity for Electrochemical CO2 Reduction. , 2017, Journal of the American Chemical Society.

[21]  Dean J. Miller,et al.  Supported Cobalt Polyphthalocyanine for High-Performance Electrocatalytic CO2 Reduction , 2017 .

[22]  Michael B. Ross,et al.  Tunable Cu Enrichment Enables Designer Syngas Electrosynthesis from CO2. , 2017, Journal of the American Chemical Society.

[23]  Md. Ariful Hoque,et al.  In Situ Polymer Graphenization Ingrained with Nanoporosity in a Nitrogenous Electrocatalyst Boosting the Performance of Polymer‐Electrolyte‐Membrane Fuel Cells , 2017, Advanced materials.

[24]  Y. Hwang,et al.  Insight into Electrochemical CO2 Reduction on Surface-Molecule-Mediated Ag Nanoparticles , 2017 .

[25]  Y. Surendranath,et al.  Tuning of Silver Catalyst Mesostructure Promotes Selective Carbon Dioxide Conversion into Fuels. , 2016, Angewandte Chemie.

[26]  Wilson A. Smith,et al.  Selective and Efficient Reduction of Carbon Dioxide to Carbon Monoxide on Oxide-Derived Nanostructured Silver Electrocatalysts. , 2016, Angewandte Chemie.

[27]  Jinlong Yang,et al.  Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel , 2016, Nature.

[28]  P. Yang,et al.  Metal-organic frameworks for electrocatalytic reduction of carbon dioxide. , 2015, Journal of the American Chemical Society.

[29]  C. Friend,et al.  Achieving Selective and Efficient Electrocatalytic Activity for CO2 Reduction Using Immobilized Silver Nanoparticles. , 2015, Journal of the American Chemical Society.

[30]  P. Yang,et al.  Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water , 2015, Science.

[31]  S. Back,et al.  Active Sites of Au and Ag Nanoparticle Catalysts for CO2 Electroreduction to CO , 2015 .

[32]  D. Vlachos,et al.  Mechanistic Insights into the Electrochemical Reduction of CO2 to CO on Nanostructured Ag Surfaces , 2015 .

[33]  Jai Hyun Koh,et al.  Oxygen Plasma Induced Hierarchically Structured Gold Electrocatalyst for Selective Reduction of Carbon Dioxide to Carbon Monoxide , 2015 .

[34]  Jens K Nørskov,et al.  Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces. , 2014, Physical chemistry chemical physics : PCCP.

[35]  Feng Jiao,et al.  A selective and efficient electrocatalyst for carbon dioxide reduction , 2014, Nature Communications.

[36]  Haifeng Lv,et al.  Monodisperse Au nanoparticles for selective electrocatalytic reduction of CO2 to CO. , 2013, Journal of the American Chemical Society.

[37]  P. Kenis,et al.  Ionic Liquid–Mediated Selective Conversion of CO2 to CO at Low Overpotentials , 2011, Science.

[38]  Frédéric Jaouen,et al.  Heat-treated Fe/N/C catalysts for O2 electroreduction: are active sites hosted in micropores? , 2006, The journal of physical chemistry. B.

[39]  Cody E. Carson,et al.  Variability in the Structures of Luminescent [2‐(Aminomethyl)pyridine]silver(I) Complexes: Effect of Ligand Ratio, Anion, Hydrogen Bonding, and π‐Stacking , 2005 .