Cu Metal Embedded in Oxidized Matrix Catalyst to Promote CO Activation and CO Dimerization for Electrochemical Reduction of CO

Overview

Journal Proc Natl Acad Sci U S A

Specialty Science

Date 2017 Jun 14

PMID 28607069

Citations 57

Authors

Hai Xiao

William A Goddard 3rd

Tao Cheng

Yuanyue Liu

Affiliations

Soon will be listed here.

Abstract

We propose and validate with quantum mechanics methods a unique catalyst for electrochemical reduction of CO (CORR) in which selectivity and activity of CO and C products are both enhanced at the borders of oxidized and metallic surface regions. This Cu metal embedded in oxidized matrix (MEOM) catalyst is consistent with observations that CuO-based electrodes improve performance. However, we show that a fully oxidized matrix (FOM) model would not explain the experimentally observed performance boost, and we show that the FOM is not stable under CO reduction conditions. This electrostatic tension between the Cu and Cu surface sites responsible for the MEOM mechanism suggests a unique strategy for designing more efficient and selective electrocatalysts for CORR to valuable chemicals (HCO), a critical need for practical environmental and energy applications.

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References

Perdew , Burke , Ernzerhof . Generalized Gradient Approximation Made Simple. Phys Rev Lett. 1996; 77(18):3865-3868. DOI: 10.1103/PhysRevLett.77.3865. View

Li C, Kanan M . CO2 reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu2O films. J Am Chem Soc. 2012; 134(17):7231-4. DOI: 10.1021/ja3010978. View

Gao S, Lin Y, Jiao X, Sun Y, Luo Q, Zhang W . Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel. Nature. 2016; 529(7584):68-71. DOI: 10.1038/nature16455. View

Montoya J, Shi C, Chan K, Norskov J . Theoretical Insights into a CO Dimerization Mechanism in CO2 Electroreduction. J Phys Chem Lett. 2015; 6(11):2032-7. DOI: 10.1021/acs.jpclett.5b00722. View

Kuhl K, Hatsukade T, Cave E, Abram D, Kibsgaard J, Jaramillo T . Electrocatalytic conversion of carbon dioxide to methane and methanol on transition metal surfaces. J Am Chem Soc. 2014; 136(40):14107-13. DOI: 10.1021/ja505791r. View

Kresse , Hafner . Ab initio molecular dynamics for liquid metals. Phys Rev B Condens Matter. 1993; 47(1):558-561. DOI: 10.1103/physrevb.47.558. View

Roberts F, Kuhl K, Nilsson A . High selectivity for ethylene from carbon dioxide reduction over copper nanocube electrocatalysts. Angew Chem Int Ed Engl. 2015; 54(17):5179-82. DOI: 10.1002/anie.201412214. View

Ma M, Djanashvili K, Smith W . Controllable Hydrocarbon Formation from the Electrochemical Reduction of CO2 over Cu Nanowire Arrays. Angew Chem Int Ed Engl. 2016; 55(23):6680-4. DOI: 10.1002/anie.201601282. View

Loiudice A, Lobaccaro P, Kamali E, Thao T, Huang B, Ager J . Tailoring Copper Nanocrystals towards C2 Products in Electrochemical CO2 Reduction. Angew Chem Int Ed Engl. 2016; 55(19):5789-92. DOI: 10.1002/anie.201601582. View

10.

Xiao H, Cheng T, Goddard 3rd W, Sundararaman R . Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111). J Am Chem Soc. 2015; 138(2):483-6. DOI: 10.1021/jacs.5b11390. View

11.

Arias , Payne , Joannopoulos . Ab initio molecular dynamics: Analytically continued energy functionals and insights into iterative solutions. Phys Rev Lett. 1992; 69(7):1077-1080. DOI: 10.1103/PhysRevLett.69.1077. View

12.

Nie X, Esopi M, Janik M, Asthagiri A . Selectivity of CO(2) reduction on copper electrodes: the role of the kinetics of elementary steps. Angew Chem Int Ed Engl. 2013; 52(9):2459-62. DOI: 10.1002/anie.201208320. View

13.

Bendavid L, Carter E . First-principles predictions of the structure, stability, and photocatalytic potential of Cu2O surfaces. J Phys Chem B. 2013; 117(49):15750-60. DOI: 10.1021/jp406454c. View

14.

Xiao H, Cheng T, Goddard 3rd W . Atomistic Mechanisms Underlying Selectivities in C(1) and C(2) Products from Electrochemical Reduction of CO on Cu(111). J Am Chem Soc. 2016; 139(1):130-136. DOI: 10.1021/jacs.6b06846. View

15.

Mistry H, Varela A, Bonifacio C, Zegkinoglou I, Sinev I, Choi Y . Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene. Nat Commun. 2016; 7:12123. PMC: 4931497. DOI: 10.1038/ncomms12123. View

16.

Schouten K, Qin Z, Perez Gallent E, Koper M . Two pathways for the formation of ethylene in CO reduction on single-crystal copper electrodes. J Am Chem Soc. 2012; 134(24):9864-7. DOI: 10.1021/ja302668n. View

17.

Lian X, Xiao P, Yang S, Liu R, Henkelman G . Calculations of oxide formation on low-index Cu surfaces. J Chem Phys. 2016; 145(4):044711. DOI: 10.1063/1.4959903. View

18.

Kas R, Kortlever R, Milbrat A, Koper M, Mul G, Baltrusaitis J . Electrochemical CO2 reduction on Cu2O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons. Phys Chem Chem Phys. 2014; 16(24):12194-201. DOI: 10.1039/c4cp01520g. View

19.

Petrosyan S, Rigos A, Arias T . Joint density-functional theory: ab initio study of Cr2O3 surface chemistry in solution. J Phys Chem B. 2006; 109(32):15436-44. DOI: 10.1021/jp044822k. View

20.

Liu H, Wang Y, Bowman J . Vibrational analysis of an ice Ih model from 0 to 4000 cm(-1) using the ab initio WHBB potential energy surface. J Phys Chem B. 2013; 117(34):10046-52. DOI: 10.1021/jp405865c. View