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      Surface passivation for highly active, selective, stable, and scalable CO 2 electroreduction

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          Abstract

          Electrochemical conversion of CO 2 to formic acid using Bismuth catalysts is one the most promising pathways for industrialization. However, it is still difficult to achieve high formic acid production at wide voltage intervals and industrial current densities because the Bi catalysts are often poisoned by oxygenated species. Herein, we report a Bi 3S 2 nanowire-ascorbic acid hybrid catalyst that simultaneously improves formic acid selectivity, activity, and stability at high applied voltages. Specifically, a more than 95% faraday efficiency was achieved for the formate formation over a wide potential range above 1.0 V and at ampere-level current densities. The observed excellent catalytic performance was attributable to a unique reconstruction mechanism to form more defective sites while the ascorbic acid layer further stabilized the defective sites by trapping the poisoning hydroxyl groups. When used in an all-solid-state reactor system, the newly developed catalyst achieved efficient production of pure formic acid over 120 hours at 50 mA cm –2 (200 mA cell current).

          Abstract

          Achieving high pure formic acid production from CO 2 electroconversion is of high interest yet challenging. Here the authors report vitamin C functionalized Bi 3S 2 nanowire catalyst to achieve selective, active, and stable formic acid production.

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          Most cited references66

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          Efficient iterative schemes forab initiototal-energy calculations using a plane-wave basis set

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            Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set

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              A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu.

              The method of dispersion correction as an add-on to standard Kohn-Sham density functional theory (DFT-D) has been refined regarding higher accuracy, broader range of applicability, and less empiricism. The main new ingredients are atom-pairwise specific dispersion coefficients and cutoff radii that are both computed from first principles. The coefficients for new eighth-order dispersion terms are computed using established recursion relations. System (geometry) dependent information is used for the first time in a DFT-D type approach by employing the new concept of fractional coordination numbers (CN). They are used to interpolate between dispersion coefficients of atoms in different chemical environments. The method only requires adjustment of two global parameters for each density functional, is asymptotically exact for a gas of weakly interacting neutral atoms, and easily allows the computation of atomic forces. Three-body nonadditivity terms are considered. The method has been assessed on standard benchmark sets for inter- and intramolecular noncovalent interactions with a particular emphasis on a consistent description of light and heavy element systems. The mean absolute deviations for the S22 benchmark set of noncovalent interactions for 11 standard density functionals decrease by 15%-40% compared to the previous (already accurate) DFT-D version. Spectacular improvements are found for a tripeptide-folding model and all tested metallic systems. The rectification of the long-range behavior and the use of more accurate C(6) coefficients also lead to a much better description of large (infinite) systems as shown for graphene sheets and the adsorption of benzene on an Ag(111) surface. For graphene it is found that the inclusion of three-body terms substantially (by about 10%) weakens the interlayer binding. We propose the revised DFT-D method as a general tool for the computation of the dispersion energy in molecules and solids of any kind with DFT and related (low-cost) electronic structure methods for large systems.
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                Author and article information

                Contributors
                chuan.xia@uestc.edu.cn
                ziyun.wang@auckland.ac.nz
                l.dai@unsw.edu.au
                mlq518@whut.edu.cn
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                3 August 2023
                3 August 2023
                2023
                : 14
                : 4670
                Affiliations
                [1 ]GRID grid.162110.5, ISNI 0000 0000 9291 3229, State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, , Wuhan University of Technology, ; Wuhan, 430070 Hubei P. R. China
                [2 ]GRID grid.83440.3b, ISNI 0000000121901201, Electrochemical Innovation Lab, Department of Chemical Engineering, , University College London, ; London, WC1E 7JE UK
                [3 ]GRID grid.9654.e, ISNI 0000 0004 0372 3343, School of Chemical Sciences, , The University of Auckland, ; Auckland, 1010 New Zealand
                [4 ]GRID grid.1005.4, ISNI 0000 0004 4902 0432, Australian Carbon Materials Centre (A-CMC), School of Chemical Engineering, , University of New South Wales, ; Sydney, NSW 2052 Australia
                [5 ]GRID grid.54549.39, ISNI 0000 0004 0369 4060, School of Materials and Energy, , University of Electronic Science and Technology of China, ; Chengdu, P. R. China
                [6 ]GRID grid.162110.5, ISNI 0000 0000 9291 3229, International School of Materials Science and Engineering, , Wuhan University of Technology, ; Wuhan, 430070 Hubei P. R. China
                [7 ]GRID grid.11135.37, ISNI 0000 0001 2256 9319, Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, , School of Materials Science and Engineering, Peking University, ; Beijing, 100871 P. R. China
                [8 ]GRID grid.9227.e, ISNI 0000000119573309, Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, , Chinese Academy of Sciences, ; Shanghai, 201210 P. R. China
                [9 ]GRID grid.162110.5, ISNI 0000 0000 9291 3229, Hubei Longzhong Laboratory, , Wuhan University of Technology (Xiangyang Demonstration Zone), ; Xiangyang, 441000 Hubei P. R. China
                Author information
                http://orcid.org/0000-0003-1629-240X
                http://orcid.org/0000-0003-2277-849X
                http://orcid.org/0000-0001-8405-5962
                http://orcid.org/0000-0002-8317-2080
                http://orcid.org/0000-0001-6826-9987
                http://orcid.org/0000-0001-6756-3578
                http://orcid.org/0000-0002-7365-9645
                http://orcid.org/0000-0003-0712-6952
                http://orcid.org/0000-0002-1234-4455
                http://orcid.org/0000-0003-4526-159X
                http://orcid.org/0000-0002-2817-8367
                http://orcid.org/0000-0001-7536-160X
                http://orcid.org/0000-0003-4259-7725
                Article
                40342
                10.1038/s41467-023-40342-6
                10400642
                37537180
                84f295f2-4375-4913-9c12-9ec41a676aeb
                © Springer Nature Limited 2023

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 3 February 2023
                : 24 July 2023
                Funding
                Funded by: FundRef https://doi.org/10.13039/501100001809, National Natural Science Foundation of China (National Science Foundation of China);
                Award ID: 51832004
                Award ID: 52127816
                Award Recipient :
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                © Springer Nature Limited 2023

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                electrocatalysis
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                electrocatalysis

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