High-Throughput Screening of a Single-Atom Alloy for Electroreduction of Dinitrogen to Ammonia.

Exploring electrocatalysts with high activity, selectivity, and stability is essential for the development of applicable electrocatalytic ammonia synthesis technology. By performing density functional theory calculations, we systematically investigated the potential of a series of transition-metal-doped Au-based single-atom alloys (SAAs) as promising electrocatalysts for nitrogen reduction reaction (NRR). The overall process for the Au-based electrocatalyst suffers from the limiting potential arising from the first hydrogenation step of the reduction of *N2 to *NNH. However, SAAs showed to be favorable toward lowering free energy barriers by increasing the binding strength of N2. According to simulation results, three descriptors were proposed to describe the first hydrogenation step ΔG(*N2 → *NNH): ΔG(*NNH), d-band center, and d/√Em. Eight doped elements (Ti, V, Nb, Ru, Ta, Os, W, and Mo) were initially screened out with a limiting potential ranging from -0.75 to -0.30 V. Particularly, Mo- and W-doped systems possess the best activity with a limiting potential of -0.30 V each. Then, the intrinsic relationship between the structure and potential performance was analyzed using machine learning. The selectivity, feasibility, and stability of these candidates were also evaluated, confirming that SAA containing Mo, Ru, Ta, and W could be outstanding NRR electrocatalysts. This work not only broadens our understanding of SAA application in electrocatalysis, but also leads to the discovery of novel NRR electrocatalysts.

[1]  Shiping Huang,et al.  Establishing a Theoretical Landscape for Identifying Basal Plane Active 2D Metal Borides (MBenes) toward Nitrogen Electroreduction , 2020, Advanced Functional Materials.

[2]  M. Stamatakis,et al.  Controlling Hydrocarbon (De)Hydrogenation Pathways with Bifunctional PtCu Single-Atom Alloys. , 2020, The journal of physical chemistry letters.

[3]  Christine M. Gabardo,et al.  Enhanced multi-carbon alcohol electroproduction from CO via modulated hydrogen adsorption , 2020, Nature Communications.

[4]  G. Giannakakis,et al.  Single-Atom Alloy Catalysis. , 2020, Chemical reviews.

[5]  Yi Luo,et al.  Synergistic Effect of Surface Terminated Oxygen Vacancy and Single Atom Catalysts on Defective MXenes for Efficient Nitrogen Fixation. , 2020, The journal of physical chemistry letters.

[6]  Yuen Wu,et al.  Highly Productive Electrosynthesis of Ammonia by Admolecule-Targeting Single Ag Sites. , 2020, ACS nano.

[7]  Jianguo Wang,et al.  High-Throughput Screening of Hydrogen Evolution Reaction Catalysts in MXene Materials , 2020, The Journal of Physical Chemistry C.

[8]  Thomas W. Hamann,et al.  Recent Advances and Challenges of Electrocatalytic N2 Reduction to Ammonia. , 2020, Chemical reviews.

[9]  Yadong Li,et al.  Isolated Ni atoms dispersed on Ru nanosheets: high performance electrocatalysts toward hydrogen oxidation reaction. , 2020, Nano letters.

[10]  Y. Chai,et al.  Computational Design of Transition Metal Single Atom Electrocatalysts on PtS2 for Efficient Nitrogen Reduction. , 2020, ACS applied materials & interfaces.

[11]  Yi Du,et al.  Efficient Ammonia Electrosynthesis from Nitrate on Strained Ruthenium Nanoclusters. , 2020, Journal of the American Chemical Society.

[12]  Q. Jiang,et al.  Determining the adsorption energies of small molecules with the intrinsic properties of adsorbates and substrates , 2020, Nature Communications.

[13]  Shiping Huang,et al.  Tackling the Activity and Selectivity Challenges of Electrocatalysts towards Nitrogen Reduction Reaction via Atomically Dispersed Bi-Atom Catalysts. , 2020, Journal of the American Chemical Society.

[14]  A. Vourros,et al.  An Electrochemical Haber-Bosch Process , 2020 .

[15]  Haibo Yu,et al.  Theoretical Screening of Single Transition Metal Atoms Embedded in MXene Defects as Superior Electrocatalyst of Nitrogen Reduction Reaction , 2019, Small Methods.

[16]  Shiping Huang,et al.  Simultaneously Achieving High Activity and Selectivity toward Two-Electron O2 Electroreduction: The Power of Single-Atom Catalysts , 2019, ACS Catalysis.

[17]  Haibo Yu,et al.  Theoretical Investigation on The Single Transition Metal Atom Decorated Defective MoS2 for Electrocatalytic Ammonia Synthesis. , 2019, ACS applied materials & interfaces.

[18]  Tim Mueller,et al.  Ensemble Effect in Bimetallic Electrocatalysts for CO2 Reduction. , 2019, Journal of the American Chemical Society.

[19]  V. Wang,et al.  VASPKIT: A Pre- and Post-Processing Program for VASP code , 2019 .

[20]  Matthew M. Montemore,et al.  Integrated Catalysis-Surface Science-Theory Approach to Understand Selectivity in the Hydrogenation of 1-Hexyne to 1-Hexene on PdAu Single-Atom Alloy Catalysts , 2019, ACS Catalysis.

[21]  Brian A. Rohr,et al.  Strategies toward Selective Electrochemical Ammonia Synthesis , 2019, ACS Catalysis.

[22]  Douglas R. MacFarlane,et al.  Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia , 2019, Nature Catalysis.

[23]  Yong Wang,et al.  Catalysis with Two-Dimensional Materials Confining Single Atoms: Concept, Design, and Applications. , 2019, Chemical reviews.

[24]  Haihui Wang,et al.  Nitrogen Fixation by Ru Single-Atom Electrocatalytic Reduction , 2019, Chem.

[25]  Jinlan Wang,et al.  A General Two‐Step Strategy–Based High‐Throughput Screening of Single Atom Catalysts for Nitrogen Fixation , 2018, Small Methods.

[26]  G. Giannakakis,et al.  Single-Atom Alloys as a Reductionist Approach to the Rational Design of Heterogeneous Catalysts. , 2018, Accounts of chemical research.

[27]  M. Shu,et al.  N2 Electrochemical Reduction: Achieving a Record‐High Yield Rate of 120.9 μgNH3  mgcat.−1  h−1 for N2 Electrochemical Reduction over Ru Single‐Atom Catalysts (Adv. Mater. 40/2018) , 2018, Advanced Materials.

[28]  S. Back,et al.  Suppression of Hydrogen Evolution Reaction in Electrochemical N2 Reduction Using Single-Atom Catalysts: A Computational Guideline , 2018, ACS Catalysis.

[29]  Ross D. Milton,et al.  Catalysts for nitrogen reduction to ammonia , 2018, Nature Catalysis.

[30]  D. Cao,et al.  A universal principle for a rational design of single-atom electrocatalysts , 2018, Nature Catalysis.

[31]  Hiang Kwee Lee,et al.  Favoring the unfavored: Selective electrochemical nitrogen fixation using a reticular chemistry approach , 2018, Science Advances.

[32]  Rian D. Dewhurst,et al.  Nitrogen fixation and reduction at boron , 2018, Science.

[33]  Matthew T. Darby,et al.  Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation. , 2018, Nature chemistry.

[34]  E. Carter,et al.  Prediction of a low-temperature N2 dissociation catalyst exploiting near-IR–to–visible light nanoplasmonics , 2017, Science Advances.

[35]  Michael Walter,et al.  The atomic simulation environment-a Python library for working with atoms. , 2017, Journal of physics. Condensed matter : an Institute of Physics journal.

[36]  Jun Jiang,et al.  Isolation of Cu Atoms in Pd Lattice: Forming Highly Selective Sites for Photocatalytic Conversion of CO2 to CH4. , 2017, Journal of the American Chemical Society.

[37]  Colin F. Dickens,et al.  Combining theory and experiment in electrocatalysis: Insights into materials design , 2017, Science.

[38]  Thomas F. Jaramillo,et al.  Electrochemical Ammonia Synthesis-The Selectivity Challenge , 2017 .

[39]  E. Carter,et al.  Thermodynamic Constraints in Using AuM (M = Fe, Co, Ni, and Mo) Alloys as N₂ Dissociation Catalysts: Functionalizing a Plasmon-Active Metal. , 2016, ACS nano.

[40]  Joseph H. Montoya,et al.  The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations. , 2015, ChemSusChem.

[41]  Kendra Letchworth-Weaver,et al.  Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. , 2013, The Journal of chemical physics.

[42]  Tao Zhang,et al.  Single-atom catalysts: a new frontier in heterogeneous catalysis. , 2013, Accounts of chemical research.

[43]  E. A. Lewis,et al.  Isolated Metal Atom Geometries as a Strategy for Selective Heterogeneous Hydrogenations , 2012, Science.

[44]  Min Yu,et al.  Accurate and efficient algorithm for Bader charge integration. , 2010, The Journal of chemical physics.

[45]  Stefan Grimme,et al.  Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction , 2006, J. Comput. Chem..

[46]  W. Schmickler,et al.  d-Band catalysis in electrochemistry. , 2006, Chemphyschem : a European journal of chemical physics and physical chemistry.

[47]  H. Jónsson,et al.  Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode. , 2004, The journal of physical chemistry. B.

[48]  Robert P. Sheridan,et al.  Random Forest: A Classification and Regression Tool for Compound Classification and QSAR Modeling , 2003, J. Chem. Inf. Comput. Sci..

[49]  G. Kyriacou,et al.  Electrochemical synthesis of ammonia at atmospheric pressure and low temperature in a solid polymer electrolyte cell , 2000 .