De Luna, Phil
Dinh, Cao Thang
Chan, Ting Shan
Sham, Tsun Kong
Hwang, Bing Joe
Sargent, Edward H.
KAUST DepartmentAdvanced Membranes & Porous Materials Center
Advanced Membranes and Porous Materials Research Center
Chemical Science Program
Imaging & Characterization Laboratory
Imaging and Characterization Core Lab
KAUST Catalysis Center
KAUST Catalysis Center (KCC)
Nanostructured Functional Materials (NFM) laboratory
Physical Science and Engineering (PSE) Division
Online Publication Date2019-06-25
Print Publication Date2019-07
Embargo End Date2020-07-17
Permanent link to this recordhttp://hdl.handle.net/10754/656210
MetadataShow full item record
AbstractDefect sites are often proposed as key active sites in the design of catalysts. A promising strategy for improving activity is to achieve a high density of homogeneously dispersed atomic defects; however, this is seldom accomplished in metals. We hypothesize that vacancy-rich catalysts could be obtained through the synthesis of quantum dots (QDs) and their electrochemical reduction during the CO2 reduction reaction (CO2RR). Here, we report that QD-derived catalysts (QDDCs) with up to 20 vol % vacancies achieve record current densities of 16, 19, and 25 mAcm−2 with high faradic efficiencies in the electrosynthesis of formate, carbon monoxide, and ethylene at low potentials of –0.2, –0.3, and –0.9 V versus reversible hydrogen electrode (RHE), respectively. The materials are stable after 80 hr of CO2RR. These CO2RR performances in aqueous solution surpass those of previously reported catalysts by 2×. Together, X-ray absorption spectroscopy and computational studies reveal that the vacancies produce a local atomic and electronic structure that enhances CO2RR.
CitationLiu, M., Liu, M., Wang, X., Kozlov, S. M., Cao, Z., De Luna, P., … Sargent, E. H. (2019). Quantum-Dot-Derived Catalysts for CO2 Reduction Reaction. Joule, 3(7), 1703–1718. doi:10.1016/j.joule.2019.05.010
SponsorsThis work was supported financially by the National Natural Science Foundation of China (21872174), International S&T Cooperation Program of China (2017YFE0127800), the Ontario Research Fund Research-Excellence Program, the Natural Sciences and Engineering Research Council (NSERC) of Canada, the Canadian Institute for Advanced Research Bio-inspired Solar Energy program, a University of Toronto Connaught grant, the Ministry of Science and Technology of Taiwan, the King Abdullah University of Science and Technology (KAUST), the Project of Innovation-Driven Plan in Central South University (2017CX003, 20180018050001), the Hunan Provincial Science and Technology Program (2017XK2026), the State Key Laboratory of Powder Metallurgy in Central South University, the Shenzhen Science and Technology Innovation Project (JCYJ20180307151313532, JCYJ20180307164633296), the Thousand Youth Talents Plan of China, and the Hundred Youth Talents Program of Hunan. S.M.K. Z.C. and L.C. thank the KAUST Supercomputing Laboratory for the resources provided. This work benefited from Taiwan Beam Lines BL01C1, BL07A1, and BL17C1 in the National Synchrotron Radiation Research Center, the Soft X-Ray Microcharacterization Beamline at Canadian Light Source (CLS) and Sector 20-BM at the Advanced Photon Source (APS). The authors thank Y. Pang, J. Fan, O.Voznyy, J. Xu, F. Arquer, T. Safaei, A. Klinkova, R. Wolowiec, D. Kopilovic, L. Levina, J. Tam, S. Boccia, and S. Hoogland from U of T for fruitful discussions; Y. Hu from CLS; Z. Finfrock and M. Ward from APS; and C. Xiao from the University of Science and Technology of China for their help during the study. Min Liu, E.H.S. and B.-J.H. supervised the project. Min Liu, Mengxia Liu, and X.W. designed the experiments. S.M.K. Z.C. and L.C. carried out electrochemical simulations. S.M.K. Z.C. and L.C. carried out electrochemical simulations. P.D.L. and A.S. carried out simulations of vacancy formation energies. Mengxia Liu, X.L. P.W. and H.L. synthesized quantum dots and did ligand exchange. Min Liu, X.W. Z.W. T.-S.C. T.-K.S. and B.-J.H. performed the X-ray measurements. Y.Y. carried out in situ Raman measurements. D.Z. and Y.H. performed the TEM measurements. H.L. and K.L. carried out the XPS measurements. X.Q. J.H, C.J. H.Z. M.Z. Y.Z. C.T.D. and C.Z. performed electrochemical measurements. All authors discussed the results and assisted during manuscript preparation. The authors declare no competing interests.
Except where otherwise noted, this item's license is described as NOTICE: this is the author’s version of a work that was accepted for publication in Joule. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Joule, [[Volume], [Issue], (2019-07-17)] DOI: 10.1016/j.joule.2019.05.010 . © 2019. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/