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SCIENCE CHINA Materials, Volume 63 , Issue 12 : 2606-2612(2020) https://doi.org/10.1007/s40843-020-1440-6

N-modulated Cu+ for efficient electrochemical carbon monoxide reduction to acetate

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  • ReceivedMay 20, 2020
  • AcceptedJun 25, 2020
  • PublishedSep 7, 2020

Abstract


Funding

the Ministry of Science and Technology(2016YFA0203302)

the National Natural Science Foundation of China(21875042,21634003,51573027,21975148)

Science and Technology Commission of Shanghai Municipality(16JC1400702,18QA1400800)

Shanghai Municipal Education Commission(2017-01-07-00-07-E00062)

the Program of Eastern Scholar at Shanghai Institutions and the Yanchang Petroleum Group

the Natural Science Foundation of Jiangsu Higher Education Institutions(SBK20190810)

the Jiangsu Province High-Level Talents(JNHB-106)

the China Postdoctoral Science Foundation(2019M660128)

the start-up supports of Soochow University and the Program for Jiangsu Specially-Appointed Professors

and the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)


Acknowledgment

This work was supported by the Ministry of Science and Technology (2016YFA0203302), the National Natural Science Foundation of China (21875042, 21634003, 51573027 and 21975148), the Science and Technology Commission of Shanghai Municipality (16JC1400702 and 18QA1400800), Shanghai Municipal Education Commission (2017-01-07-00-07-E00062), the Program of Eastern Scholar at Shanghai Institutions and Yanchang Petroleum Group, the Natural Science Foundation of Jiangsu Higher Education Institutions (SBK20190810), Jiangsu Province High-Level Talents (JNHB-106), the China Postdoctoral Science Foundation (2019M660128), the start-up supports of Soochow University and the Program for Jiangsu Specially-Appointed Professors, and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD). We acknowledge Shanghai Supercomputer Center for providing the computational resources, and Collaborative Innovation Center of Suzhou Nano Science & Technology for this work. This work also benefited from the 4B9B beamlines at Beijing Synchrotron Radiation Facility (BSRF).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Peng H, Zhang B and Cheng T supervised the project. Yang H and Cheng T performed the DFT simulations. Ni F and Wen Y carried out the synthesis of catalysts and electrochemical measurements. Bai H and Zhang L performed the TEM experiments. Cui C, Li S and He S performed the sXAS experiments. All authors discussed the results and helped with the the manuscript preparation.


Author information

Fenglou Ni received his BE in functional materials from Huazhong University of Science and Technology in 2017. He is a Master candidate in the Laboratory of Advanced Materials at Fudan University. His research is focused on electrochemistry, energy conversion and storage.


Bo Zhang received his BE in applied physics from Northwestern Polytechnical University in 2006, and his PhD in chemical engineering and technology from East China University of Science and Technology in 2011. He then worked at East China University of Science and Technology from 2011 to 2015, and the University of Toronto from 2015 to 2017. He is currently a full professor in the Department of Macromolecular Science at Fudan University. His research is focused on electrochemistry, energy conversion and storage.


Supplementary data

Supplementary information

Experimental details and supporting data are available in the online version of the paper.


References

[1] Jhong HR, Ma S, Kenis PJ. Electrochemical conversion of CO2 to useful chemicals: current status, remaining challenges, and future opportunities. Curr Opin Chem Eng, 2013, 2191-199 CrossRef Google Scholar

[2] Jouny M, Luc W, Jiao F. General techno-economic analysis of CO2 electrolysis systems. Ind Eng Chem Res, 2018, 572165-2177 CrossRef Google Scholar

[3] Seh ZW, Kibsgaard J, Dickens CF, et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science, 2017, 355eaad4998 CrossRef Google Scholar

[4] Ma M, Trześniewski BJ, Xie J, et al. Selective and efficient reduction of carbon dioxide to carbon monoxide on oxide-derived nanostructured silver electrocatalysts. Angew Chem Int Ed, 2016, 559748-9752 CrossRef Google Scholar

[5] Liu M, Pang Y, Zhang B, et al. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration. Nature, 2016, 537382-386 CrossRef Google Scholar

[6] Won DH, Shin H, Koh J, et al. Highly efficient, selective, and stable CO2 electroreduction on a hexagonal Zn catalyst. Angew Chem Int Ed, 2016, 559297-9300 CrossRef Google Scholar

[7] He S, Ni F, Ji Y, et al. The p-orbital delocalization of main-group metals to boost CO2 electroreduction. Angew Chem Int Ed, 2018, 5716114-16119 CrossRef Google Scholar

[8] Gao S, Jiao X, Sun Z, et al. Ultrathin Co3O4 layers realizing optimized CO2 electroreduction to formate. Angew Chem Int Ed, 2016, 55698-702 CrossRef Google Scholar

[9] Klinkova A, De Luna P, Dinh CT, et al. Rational design of efficient palladium catalysts for electroreduction of carbon dioxide to formate. ACS Catal, 2016, 68115-8120 CrossRef Google Scholar

[10] Mistry H, Varela AS, Bonifacio CS, et al. Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene. Nat Commun, 2016, 712123 CrossRef Google Scholar

[11] Dinh CT, Burdyny T, Kibria MG, et al. CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. Science, 2018, 360783-787 CrossRef Google Scholar

[12] Bai H, Cheng T, Li S, et al. Controllable CO adsorption determines ethylene and methane productions from CO2 electroreduction. Sci Bull, 2020, doi: 10.1016/j.scib.2020.06.023 CrossRef Google Scholar

[13] Li YC, Wang Z, Yuan T, et al. Binding site diversity promotes CO2 electroreduction to ethanol. J Am Chem Soc, 2019, 1418584-8591 CrossRef Google Scholar

[14] Hoang TTH, Verma S, Ma S, et al. Nanoporous copper–silver alloys by additive-controlled electrodeposition for the selective electroreduction of CO2 to ethylene and ethanol. J Am Chem Soc, 2018, 1405791-5797 CrossRef Google Scholar

[15] Ma S, Sadakiyo M, Heima M, et al. Electroreduction of carbon dioxide to hydrocarbons using bimetallic Cu–Pd catalysts with different mixing patterns. J Am Chem Soc, 2017, 13947-50 CrossRef Google Scholar

[16] Munir S, Varzeghani AR, Kaya S. Electrocatalytic reduction of CO2 to produce higher alcohols. Sustain Energy Fuels, 2018, 22532-2541 CrossRef Google Scholar

[17] Wang Y, Wang D, Dares CJ, et al. CO2 reduction to acetate in mixtures of ultrasmall (Cu)n,(Ag)m bimetallic nanoparticles. Proc Natl Acad Sci USA, 2018, 115278-283 CrossRef Google Scholar

[18] Li CW, Ciston J, Kanan MW. Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper. Nature, 2014, 508504-507 CrossRef Google Scholar

[19] Jouny M, Luc W, Jiao F. High-rate electroreduction of carbon monoxide to multi-carbon products. Nat Catal, 2018, 1748-755 CrossRef Google Scholar

[20] Luc W, Fu X, Shi J, et al. Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate. Nat Catal, 2019, 2423-430 CrossRef Google Scholar

[21] Liu X, Xiao J, Peng H, et al. Understanding trends in electrochemical carbon dioxide reduction rates. Nat Commun, 2017, 815438 CrossRef Google Scholar

[22] Kortlever R, Shen J, Schouten KJP, et al. Catalysts and reaction pathways for the electrochemical reduction of carbon dioxide. J Phys Chem Lett, 2015, 64073-4082 CrossRef Google Scholar

[23] Ou L, Long W, Chen Y, et al. New reduction mechanism of CO dimer by hydrogenation to C2H4 on a Cu(100) surface: theoretical insight into the kinetics of the elementary steps. RSC Adv, 2015, 596281-96289 CrossRef Google Scholar

[24] Zhuang TT, Liang ZQ, Seifitokaldani A, et al. Steering post-C–C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi-carbon alcohols. Nat Catal, 2018, 1421-428 CrossRef Google Scholar

[25] Zhuang TT, Pang Y, Liang ZQ, et al. Copper nanocavities confine intermediates for efficient electrosynthesis of C3 alcohol fuels from carbon monoxide. Nat Catal, 2018, 1946-951 CrossRef Google Scholar

[26] Kim D, Kley CS, Li Y, et al. Copper nanoparticle ensembles for selective electroreduction of CO2 to C2–C3 products. Proc Natl Acad Sci USA, 2017, 11410560-10565 CrossRef Google Scholar

[27] Zhou Y, Che F, Liu M, et al. Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons. Nat Chem, 2018, 10974-980 CrossRef Google Scholar

[28] Xiao H, Goddard Iii WA, Cheng T, et al. Cu metal embedded in oxidized matrix catalyst to promote CO2 activation and CO dimerization for electrochemical reduction of CO2. Proc Natl Acad Sci USA, 2017, 114201702405 CrossRef Google Scholar

[29] Lee S, Kim D, Lee J. Electrocatalytic production of C3–C4 compounds by conversion of CO2 on a chloride-induced bi-phasicCu2O-Cu catalyst. Angew Chem Int Ed, 2015, 5414701-14705 CrossRef Google Scholar

[30] Liang ZQ, Zhuang TT, Seifitokaldani A, et al. Copper-on-nitride enhances the stable electrosynthesis of multi-carbon products from CO2. Nat Commun, 2018, 93828 CrossRef Google Scholar

[31] Yin Z, Yu C, Zhao Z, et al. Cu3N Nanocubes for selective electrochemical reduction of CO2 to ethylene. Nano Lett, 2019, 198658-8663 CrossRef Google Scholar

[32] Liu Y, Chen S, Quan X, et al. Efficient electrochemical reduction of carbon dioxide to acetate on nitrogen-doped nanodiamond. J Am Chem Soc, 2015, 13711631-11636 CrossRef Google Scholar

[33] Cheng T, Fortunelli A, Goddard Iii WA. Reaction intermediates during operando electrocatalysis identified from full solvent quantum mechanics molecular dynamics. Proc Natl Acad Sci USA, 2019, 1167718-7722 CrossRef Google Scholar

[34] Lum Y, Cheng T, Goddard Iii WA, et al. Electrochemical CO reduction builds solvent water into oxygenate products. J Am Chem Soc, 2018, 1409337-9340 CrossRef Google Scholar

[35] Cai J, Song Y, Zang Y, et al. N-induced lattice contraction generally boosts the hydrogen evolution catalysis of P-rich metal phosphides. Sci Adv, 2020, 6eaaw8113 CrossRef Google Scholar

[36] Sham TK, Hiraya A, Watanabe M. Electronic structure of Cu-Au alloys from the Cu perspective: A CuL3,2-edge study. Phys Rev B, 1997, 557585-7592 CrossRef Google Scholar

[37] Li J, Che F, Pang Y, et al. Copper adparticle enabled selective electrosynthesis of n-propanol. Nat Commun, 2018, 94614 CrossRef Google Scholar

[38] Hulbert SL, Bunker BA, Brown FC, et al. Copper L2,3 near-edge structure in Cu2O. Phys Rev B, 1984, 302120-2126 CrossRef Google Scholar

[39] Ripatti DS, Veltman TR, Kanan MW. Carbon monoxide gas diffusion electrolysis that produces concentrated C2 products with high single-pass conversion. Joule, 2019, 3240-256 CrossRef Google Scholar

[40] Feng X, Jiang K, Fan S, et al. A direct grain-boundary-activity correlation for CO electroreduction on Cu nanoparticles. ACS Cent Sci, 2016, 2169-174 CrossRef Google Scholar

[41] Li J, Chang K, Zhang H, et al. Effectively increased efficiency for electroreduction of carbon monoxide using supported polycrystalline copper powder electrocatalysts. ACS Catal, 2019, 94709-4718 CrossRef Google Scholar

[42] Zhang L, Yuan H, Wang L, et al. The critical role of electrochemically activated adsorbates in neutral OER. Sci China Mater, 2020, 632509-2516 CrossRef Google Scholar

[43] Xiao H, Cheng T, Goddard Iii WA, et al. Mechanistic explanation of the pH dependence and onset potentials for hydrocarbon products from electrochemical reduction of CO on Cu (111). J Am Chem Soc, 2016, 138483-486 CrossRef Google Scholar

  • Figure 1

    Schematic illustration of acetate electrosynthesis process. (a) Schematic illustration for the synthesis process of acetate using N-Cu catalyst, and the comparison of DOS between pristine Cu and N-Cu systems, where EF refers to Fermi level. Color code: Cu (brown), N (blue), C (light gray), O (red). (b) Bader charge analysis of the first layer Cu atoms from the constructed N-Cu model. (c) Free energy profiles of acetate formation on Cu (111) and N-Cu (111) surface, respectively. The optimized structures of key intermediates during CORR on N-Cu (111) are shown in the reaction cycle.

  • Figure 2

    The structural characterizations of N-Cu and Com-Cu. (a) TEM image of N-Cu. (b, c) The HRTEM images of N-Cu (b) and Com-Cu (c). (d) XRD patterns of Com-Cu and N-Cu and the partial magnification of the corresponding diffraction peaks of the (111) facet. (e) XPS N 1s spectra of Com-Cu and N-Cu.

  • Figure 3

    Characterizations of the surface chemical state of Cu in catalysts after reaction. (a, b) XPS Cu 2p and N 1s spectra of Com-Cu and N-Cu after 30-min reduction of CO, respectively. (c) Soft XAS of Cu L3-edge for Com-Cu and N-Cu after CORR for 30 min.

  • Figure 4

    CO reduction performances of N-Cu and Com-Cu in a flow cell system. (a, b) FEs of CORR products on N-Cu (a) and Com-Cu (b) at various applied potentials in 2 mol L−1 KOH electrolyte. (c, d) The electrochemical reduction of CO polarization curves (c) and acetate partial current densities versus applied potentials (d) of Com-Cu and N-Cu. (e) The comparison of FEs and partial current densities for acetate between this work and state-of-the-art CO reduction systems [19,20,3941]. (f) Tafel slopes derived from partial current densities for Com-Cu and N-Cu.

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