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The local coordination environment of catalysts has been investigated for an extended period to obtain enhanced catalytic performance. Especially with the advancement of single-atom catalysts (SACs), research on the coordination environment has been advanced to the atomic level. The surrounding coordination atoms of central metal atoms play important roles in their catalytic activity, selectivity and stability. In recent years, remarkable improvements of the catalytic performance of SACs have been achieved by the tailoring of coordination atoms, coordination numbers and second- or higher-coordination shells, which provided new opportunities for the further development of SACs. In this review, the characterization of coordination environment, tailoring of the local coordination environment, and their related adjustable catalytic performance will be discussed. We hope this review will provide new insights on further research of SACs.


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Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance

Show Author's information Xinyuan Li1,2Hongpan Rong1( )Jiatao Zhang1Dingsheng Wang2( )Yadong Li2
Beijing Key Laboratory of Construction-Tailorable Advanced Functional Materials and Green Applications Experimental Center of Advanced Materials, School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, China
Department of Chemistry, Tsinghua University, Beijing 100084, China

Abstract

The local coordination environment of catalysts has been investigated for an extended period to obtain enhanced catalytic performance. Especially with the advancement of single-atom catalysts (SACs), research on the coordination environment has been advanced to the atomic level. The surrounding coordination atoms of central metal atoms play important roles in their catalytic activity, selectivity and stability. In recent years, remarkable improvements of the catalytic performance of SACs have been achieved by the tailoring of coordination atoms, coordination numbers and second- or higher-coordination shells, which provided new opportunities for the further development of SACs. In this review, the characterization of coordination environment, tailoring of the local coordination environment, and their related adjustable catalytic performance will be discussed. We hope this review will provide new insights on further research of SACs.

Keywords: coordination environment, energy conversion, single-atom catalysts, catalytic performance

References(125)

[1]
Chen, Y. J.; Ji, S. F.; Chen, C.; Peng, Q.; Wang, D. S.; Li, Y. D. Single-atom catalysts: Synthetic strategies and electrochemical applications. Joule 2018, 2, 1242-1264.
[2]
Yang, X. F.; Wang, A. Q.; Qiao, B. T.; Li, J.; Liu, J. Y.; Zhang, T. Single-atom catalysts: A new frontier in heterogeneous catalysis. Acc. Chem. Res. 2013, 46, 1740-1748.
[3]
Jia, Y.; Jiang, K.; Wang, H. T.; Yao, X. D. The role of defect sites in nanomaterials for electrocatalytic energy conversion. Chem 2019, 5, 1371-1397.
[4]
Cook, S. A.; Borovik, A. S. Molecular designs for controlling the local environments around metal ions. Acc. Chem. Res. 2015, 48, 2407-2414.
[5]
Tao, L.; Wang, Y. Q.; Zou, Y. Q.; Zhang, N.; Zhang, Y. Q.; Wu, Y. J.; Wang, Y. Y.; Chen, R.; Wang, S. Y. Charge transfer modulated activity of carbon-based electrocatalysts. Adv. Energy Mater. 2020, 10, 1901227.
[6]
Sun, T. T.; Xu, L. B.; Wang, D. S.; Li, Y. D. Metal organic frameworks derived single atom catalysts for electrocatalytic energy conversion. Nano Res. 2019, 12, 2067-2080.
[7]
Mao, J. J.; Li, J.; Pei, J. J.; Liu, Y.; Wang, D. S.; Li, Y. D. Structure regulation of noble-metal-based nanomaterials at an atomic level. Nano Today 2019, 26, 164-175.
[8]
Wen, J. F.; Chen, Y. J.; Ji, S. F.; Zhang, J.; Wang, D. S.; Li, Y. D. Metal-organic frameworks-derived nitrogen-doped carbon supported nanostructured PtNi catalyst for enhanced hydrosilylation of 1-octene. Nano Res. 2019, 12, 2584-2588.
[9]
Qiao, B. T.; Wang, A. Q.; Yang, X. F.; Allard, L. F.; Jiang, Z.; Cui, Y. T.; Liu, J. Y.; Li, J.; Zhang, T. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 2011, 3, 634-641.
[10]
Li, Z. J.; Wang, D. H.; Wu, Y.; Li, Y. D. Recent advances in the precise control of isolated single-site catalysts by chemical methods. Natl. Sci. Rev. 2018, 5, 673-689.
[11]
Deng, D. H.; Chen, X. Q.; Yu, L.; Wu, X.; Liu, Q. F.; Liu, Y.; Yang, H. X.; Tian, H. F.; Hu, Y. F.; Du, P. P. et al. A single iron site confined in a graphene matrix for the catalytic oxidation of benzene at room temperature. Sci. Adv. 2015, 1, e1500462.
[12]
Deng, J.; Li, H. B.; Xiao, J. P.; Tu, Y. C.; Deng, D. H.; Yang, H. X.; Tian, H. F.; Li, J. Q.; Ren, P. J.; Bao, X. H. Triggering the electrocatalytic hydrogen evolution activity of the inert two-dimensional MoS2 surface via single-atom metal doping. Energy Environ. Sci. 2015, 8, 1594-1601.
[13]
Liu, J. Y. Catalysis by supported single metal atoms. ACS Catal. 2017, 7, 34-59.
[14]
Lin, J.; Wang, X. D. Rh single atom catalyst for direct conversion of methane to oxygenates. Sci. China Mater. 2018, 61, 758-760.
[15]
Lang, R.; Xi, W.; Liu, J. C.; Cui, Y. T.; Li, T. B.; Lee, A. F.; Chen, F.; Chen, Y.; Li, L.; Li, L. et al. Non defect-stabilized thermally stable single-atom catalyst. Nat. Commun. 2019, 10, 234.
[16]
Liang, Z. B.; Guo, W. H.; Zhao, R.; Qiu, T. J.; Tabassum, H.; Zou, R. Q. Engineering atomically dispersed metal sites for electrocatalytic energy conversion. Nano Energy 2019, 64, 103917.
[17]
Liu, J.; Jin, Z.; Wang, X.; Ge, J. J.; Liu, C. P.; Xing, W. Recent advances in active sites identification and regulation of M-N/C electro-catalysts towards ORR. Sci. China Chem. 2019, 62, 669-683.
[18]
Qiao, B. T.; Liang, J. X.; Wang, A. Q.; Xu, C. Q.; Li, J.; Zhang, T.; Liu, J. J. Ultrastable single-atom gold catalysts with strong covalent metal-support interaction (CMSI). Nano Res. 2015, 8, 2913-2924.
[19]
Sun, G. D.; Zhao, Z. J.; Mu, R. T.; Zha, S. J.; Li, L. L.; Chen, S.; Zang, K. T.; Luo, J.; Li, Z. L.; Purdy, S. C. et al. Breaking the scaling relationship via thermally stable Pt/Cu single atom alloys for catalytic dehydrogenation. Nat. Commun. 2018, 9, 4454.
[20]
Marcinkowski, M. D.; Darby, M. T.; Liu, J. L.; Wimble, J. M.; Lucci, F. R.; Lee, S.; Michaelides, A.; Flytzani-Stephanopoulos, M.; Stamatakis, M.; Sykes, E. C. H. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation. Nat. Chem. 2018, 10, 325-332.
[21]
Liu, W. G.; Zhang, L. L.; Liu, X.; Liu, X. Y.; Yang, X. F.; Miao, S.; Wang, W. T.; Wang, A. Q.; Zhang, T. Discriminating catalytically active FeNx species of atomically dispersed Fe-N-C catalyst for selective oxidation of the C-H bond. J. Am. Chem. Soc. 2017, 139, 10790-10798.
[22]
Liu, M. M.; Wang, L. L.; Zhao, K. N.; Shi, S. S.; Shao, Q. S.; Zhang, L.; Sun, X. L.; Zhao, Y. F.; Zhang, J. J. Atomically dispersed metal catalysts for the oxygen reduction reaction: Synthesis, characterization, reaction mechanisms and electrochemical energy applications. Energy Environ. Sci. 2019, 12, 2890-2923.
[23]
Wang, X. Q.; Li, Z. J.; Qu, Y. T.; Yuan, T. W.; Wang, W. Y.; Wu, Y. E.; Li, Y. D. Review of metal catalysts for oxygen reduction reaction: From nanoscale engineering to atomic design. Chem 2019, 5, 1486-1511.
[24]
Tao, H. C.; Choi, C.; Ding, L. X.; Jiang, Z.; Han, Z. S.; Jia, M. W.; Fan, Q.; Gao, Y. N.; Wang, H. H.; Robertson, A. W. et al. Nitrogen fixation by Ru single-atom electrocatalytic reduction. Chem 2019, 5, 204-214.
[25]
Liu, X.; Jiao, Y.; Zheng, Y.; Jaroniec, M.; Qiao, S. Z. Building up a picture of the electrocatalytic nitrogen reduction activity of transition metal single-atom catalysts. J. Am. Chem. Soc. 2019, 141, 9664-9672.
[26]
Zhao, C. M.; Wang, Y.; Li, Z. J.; Chen, W. X.; Xu, Q.; He, D. S.; Xi, D. S.; Zhang, Q. H.; Yuan, T. W.; Qu, Y. T. et al. Solid-diffusion synthesis of single-atom catalysts directly from bulk metal for efficient CO2 reduction. Joule 2019, 3, 584-594.
[27]
Millet, M. M.; Algara-Siller, G.; Wrabetz, S.; Mazheika, A.; Girgsdies, F.; Teschner, D.; Seitz, F.; Tarasov, A.; Levchenko, S. V.; Schlögl, R. et al. Ni single atom catalysts for CO2 activation. J. Am. Chem. Soc. 2019, 141, 2451-2461.
[28]
Jiao, J. Q.; Lin, R.; Liu, S. J.; Cheong, W. C.; Zhang, C.; Chen, Z.; Pan, Y.; Tang, J. G.; Wu, K. L.; Hung, S. F. et al. Copper atom-pair catalyst anchored on alloy nanowires for selective and efficient electrochemical reduction of CO2. Nat. Chem. 2019, 11, 222-228.
[29]
Zhang, Z.; Ma, C.; Tu, Y. C.; Si, R.; Wei, J.; Zhang, S. H.; Wang, Z.; Li, J. F.; Wang, Y.; Deng, D. H. Multiscale carbon foam confining single iron atoms for efficient electrocatalytic CO2 reduction to CO. Nano Res. 2019, 12, 2313-2317.
[30]
Liu, P. X.; Zheng, N. F. Coordination chemistry of atomically dispersed catalysts. Natl. Sci. Rev. 2018, 5, 636-638.
[31]
Liu, J. C.; Tang, Y.; Wang, Y. G.; Zhang, T.; Li, J. Theoretical understanding of the stability of single-atom catalysts. Natl. Sci. Rev. 2018, 5, 638-641.
[32]
Zhu, Y. Z.; Peng, W. C.; Li, Y.; Zhang, G. L.; Zhang, F. B.; Fan, X. B. Modulating the electronic structure of single-atom catalysts on 2D nanomaterials for enhanced electrocatalytic performance. Small Methods 2019, 3, 1800438.
[33]
Wang, Y.; Chen, Z.; Shen, R.; Cao, X.; Chen, Y. G.; Chen, C.; Wang, D. S.; Peng, Q.; Li, Y. D. Pd-dispersed CuS hetero-nanoplates for selective hydrogenation of phenylacetylene. Nano Res. 2016, 9, 1209-1219.
[34]
Liang, J. X.; Yu, Q.; Yang, X. F.; Zhang, T.; Li, J. A systematic theoretical study on FeOx-supported single-atom catalysts: M1/FeOx for CO oxidation. Nano Res. 2018, 11, 1599-1611.
[35]
Gui, J.; Ji, M. W.; Liu, J. J.; Xu, M.; Zhang, J. T.; Zhu, H. S. Phosphine-initiated cation exchange for precisely tailoring composition and properties of semiconductor nanostructures: Old concept, new applications. Angew. Chem., Int. Ed. 2015, 54, 3683-3687.
[36]
Bai, B.; Xu, M.; Li, N.; Chen, W. X.; Liu, J. J.; Liu, J.; Rong, H. P.; Fenske, D.; Zhang, J. T. Semiconductor nanocrystal engineering by applying thiol- and solvent-coordinated cation exchange kinetics. Angew. Chem., Int. Ed. 2019, 58, 4852-4857.
[37]
Li, X. Y.; Iqbal, M. A.; Xu, M.; Wang, Y. C.; Wang, H. Z.; Ji, M. W.; Wan, X. D.; Slater, T. J. A.; Liu, J.; Liu, J. J. et al. Au@HgxCd1-xTe core@shell nanorods by sequential aqueous cation exchange for near-infrared photodetectors. Nano Energy 2019, 57, 57-65.
[38]
Jiang, Z. L.; Sun, W. M.; Shang, H. S.; Chen, W. X.; Sun, T. T.; Li, H. J.; Dong, J. C.; Zhou, J.; Li, Z.; Wang, Y. et al. Atomic interface effect of a single atom copper catalyst for enhanced oxygen reduction reactions. Energy Environ. Sci. 2019, 12, 3508-3514.
[39]
Zhang, J. Q.; Zhao, Y. F.; Chen, C.; Huang, Y. C.; Dong, C. L.; Chen, C. J.; Liu, R. S.; Wang, C. Y.; Yan, K.; Li, Y. D. et al. Tuning the coordination environment in single-atom catalysts to achieve highly efficient oxygen reduction reactions. J. Am. Chem. Soc. 2019, 141, 20118-20126.
[40]
Chen, W. X.; Pei, J. J.; He, C. T.; Wan, J. W.; Ren, H. L.; Wang, Y.; Dong, J. C.; Wu, K. L.; Cheong, W. C.; Mao, J. J. et al. Single tungsten atoms supported on MOF-derived N-doped carbon for robust electrochemical hydrogen evolution. Adv. Mater. 2018, 30, 1800396.
[41]
Li, Z.; Ji, S. F.; Liu, Y. W.; Cao, X.; Tian, S. B.; Chen, Y. J.; Niu, Z. Q.; Li, Y. D. Well-defined materials for heterogeneous catalysis: From nanoparticles to isolated single-atom sites. Chem. Rev. 2020, 120, 623-682.
[42]
Bordiga, S.; Groppo, E.; Agostini, G.; van Bokhoven, J. A.; Lamberti, C. Reactivity of surface species in heterogeneous catalysts probed by in situ X-ray absorption techniques. Chem. Rev. 2013, 113, 1736-1850.
[43]
Moliner, M.; Gabay, J. E.; Kliewer, C. E.; Carr, R. T.; Guzman, J.; Casty, G. L.; Serna, P.; Corma, A. Reversible transformation of Pt nanoparticles into single atoms inside high-silica chabazite zeolite. J. Am. Chem. Soc. 2016, 138, 15743-15750.
[44]
Becknell, N.; Kang, Y. J.; Chen, C.; Resasco, J.; Kornienko, N.; Guo, J. H.; Markovic, N. M.; Somorjai, G. A.; Stamenkovic, V. R.; Yang, P. D. Atomic structure of Pt3Ni nanoframe electrocatalysts by in situ X-ray absorption spectroscopy. J. Am. Chem. Soc. 2015, 137, 15817-15824.
[45]
Xiao, M. L.; Zhu, J. B.; Ma, L.; Jin, Z.; Ge, J. J.; Deng, X.; Hou, Y.; He, Q. G.; Li, J. K.; Jia, Q. Y. et al. Microporous framework induced synthesis of single-atom dispersed Fe-N-C acidic ORR catalyst and its in situ reduced Fe-N4 active site identification revealed by X-ray absorption spectroscopy. ACS Catal. 2018, 8, 2824-2832.
[46]
Wang, L. B.; Zhang, W. B.; Wang, S. P.; Gao, Z. H.; Luo, Z. H.; Wang, X.; Zeng, R.; Li, A. W.; Li, H. L.; Wang, M. L. et al. Atomic-level insights in optimizing reaction paths for hydroformylation reaction over Rh/CoO single-atom catalyst. Nat. Commun. 2016, 7, 14036.
[47]
Zhang, E. H.; Wang, T.; Yu, K.; Liu, J.; Chen, W. X.; Li, A.; Rong, H. P.; Lin, R.; Ji, S. F.; Zheng, X. S. et al. Bismuth single atoms resulting from transformation of metal-organic frameworks and their use as electrocatalysts for CO2 reduction. J. Am. Chem. Soc. 2019, 141, 16569-16573.
[48]
Matsubu, J. C.; Zhang, S. Y.; DeRita, L.; Marinkovic, N. S.; Chen, J. G.; Graham, G. W.; Pan, X. Q.; Christopher, P. Adsorbate-mediated strong metal-support interactions in oxide-supported Rh catalysts. Nat. Chem. 2017, 9, 120-127.
[49]
Lin, Y. C.; Dumcenco, D. O.; Komsa, H. P.; Niimi, Y.; Krasheninnikov, A. V.; Huang, Y. S.; Suenaga, K. Properties of individual dopant atoms in single-layer MoS2: Atomic structure, migration, and enhanced reactivity. Adv. Mater. 2014, 26, 2857-2861.
[50]
DeRita, L.; Resasco, J.; Dai, S.; Boubnov, A.; Thang, H. V.; Hoffman, A. S.; Ro, I.; Graham, G. W.; Bare, S. R.; Pacchioni, G. et al. Structural evolution of atomically dispersed Pt catalysts dictates reactivity. Nat. Mater. 2019, 18, 746-751.
[51]
Xu, H. X.; Cheng, D. J.; Cao, D. P.; Zeng, X. C. A universal principle for a rational design of single-atom electrocatalysts. Nat. Catal. 2018, 1, 339-348.
[52]
Zhu, G. Q.; Liu, F.; Wang, Y. C.; Wei, Z. D.; Wang, W. Systematic exploration of N, C coordination effects on the ORR performance of Mn-Nx doped graphene catalysts based on DFT calculations. Phys. Chem. Chem. Phys. 2019, 21, 12826-12836.
[53]
Wan, C. Z.; Duan, X. F.; Huang, Y. Molecular design of single-atom catalysts for oxygen reduction reaction. Adv. Energy Mater., in press, .
[54]
Zitolo, A.; Goellner, V.; Armel, V.; Sougrati, M. T.; Mineva, T.; Stievano, L.; Fonda, E.; Jaouen, F. Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nat. Mater. 2015, 14, 937-942.
[55]
Han, Y. H.; Wang, Y. G.; Xu, R. R.; Chen, W. X.; Zheng, L. R.; Han, A. J.; Zhu, Y. Q.; Zhang, J.; Zhang, H. B.; Luo, J. et al. Electronic structure engineering to boost oxygen reduction activity by controlling the coordination of the central metal. Energy Environ. Sci. 2018, 11, 2348-2352.
[56]
Qiu, H. J.; Ito, Y.; Cong, W. T.; Tan, Y. W.; Liu, P.; Hirata, A.; Fujita, T.; Tang, Z.; Chen, M. W. Nanoporous graphene with single-atom nickel dopants: An efficient and stable catalyst for electrochemical hydrogen production. Angew. Chem., Int. Ed. 2015, 54, 14031-14035.
[57]
Yan, H.; Cheng, H.; Yi, H.; Lin, Y.; Yao, T.; Wang, C. L.; Li, J. J.; Wei, S. Q.; Lu, J. L. Single-atom Pd1/graphene catalyst achieved by atomic layer deposition: Remarkable performance in selective hydrogenation of 1,3-butadiene. J. Am. Chem. Soc. 2015, 137, 10484-10487.
[58]
Yin, X. P.; Wang, H. J.; Tang, S. F.; Lu, X. L.; Shu, M.; Si, R.; Lu, T. B. Engineering the coordination environment of single-atom platinum anchored on graphdiyne for optimizing electrocatalytic hydrogen evolution. Angew. Chem., Int. Ed. 2018, 57, 9382-9386.
[59]
Zhu, Y. Q.; Sun, W. M.; Luo, J.; Chen, W. X.; Cao, T.; Zheng, L. R.; Dong, J. C.; Zhang, J.; Zhang, M. L.; Han, Y. H. et al. A cocoon silk chemistry strategy to ultrathin N-doped carbon nanosheet with metal single-site catalysts. Nat. Commun. 2018, 9, 3861.
[60]
Li, H. N.; Cao, C. Y.; Liu, J.; Shi, Y.; Si, R.; Gu, L.; Song, W. G. Cobalt single atoms anchored on N-doped ultrathin carbon nanosheets for selective transfer hydrogenation of nitroarenes. Sci. China Mater. 2019, 62, 1306-1314.
[61]
Zhou, S. Q.; Shang, L.; Zhao, Y. X.; Shi, R.; Waterhouse, G. I. N.; Huang, Y. C.; Zheng, L. R.; Zhang, T. R. Pd single-atom catalysts on nitrogen-doped graphene for the highly selective photothermal hydrogenation of acetylene to ethylene. Adv. Mater. 2019, 31, 1900509.
[62]
Jiang, K.; Siahrostami, S.; Zheng, T. T.; Hu, Y. F.; Hwang, S.; Stavitski, E.; Peng, Y. D.; Dynes, J.; Gangisetty, M.; Su, D. et al. Isolated Ni single atoms in graphene nanosheets for high-performance CO2 reduction. Energy Environ. Sci. 2018, 11, 893-903.
[63]
Peng, P.; Shi, L.; Huo, F.; Mi, C. X.; Wu, X. H.; Zhang, S. J.; Xiang, Z. H. A pyrolysis-free path toward superiorly catalytic nitrogen-coordinated single atom. Sci. Adv. 2019, 5, eaaw2322.
[64]
Yin, P. Q.; Yao, T.; Wu, Y.; Zheng, L. R.; Lin, Y.; Liu, W.; Ju, H. X.; Zhu, J. F.; Hong, X.; Deng, Z. X. et al. Single cobalt atoms with precise N-coordination as superior oxygen reduction reaction catalysts. Angew. Chem., Int. Ed. 2016, 55, 10800-10805.
[65]
Wang, X. X.; Cullen, D. A.; Pan, Y. T.; Hwang, S.; Wang, M. Y.; Feng, Z. X.; Wang, J. Y.; Engelhard, M. H.; Zhang, H. G.; He, Y. H. et al. Nitrogen-coordinated single cobalt atom catalysts for oxygen reduction in proton exchange membrane fuel cells. Adv. Mater. 2018, 30, 1706758.
[66]
Ji, S. F.; Chen, Y. J.; Zhao, S.; Chen, W. X.; Shi, L. J.; Wang, Y.; Dong, J. C.; Li, Z.; Li, F. W.; Chen, C. et al. Atomically dispersed ruthenium species inside metal-organic frameworks: Combining the high activity of atomic sites and the molecular sieving effect of MOFs. Angew. Chem., Int. Ed. 2019, 131, 4315-4319.
[67]
Zhao, C. M.; Dai, X. Y.; Yao, T.; Chen, W. X.; Wang, X. Q.; Wang, J.; Yang, J.; Wei, S. Q.; Wu, Y.; Li, Y. D. Ionic exchange of metal- organic frameworks to access single nickel sites for efficient electroreduction of CO2. J. Am. Chem. Soc. 2017, 139, 8078-8081.
[68]
Han, Y. H.; Wang, Y. G.; Chen, W. X.; Xu, R. R.; Zheng, L. R.; Zhang, J.; Luo, J.; Shen, R. A.; Zhu, Y. Q.; Cheong, W. C. et al. Hollow N-doped carbon spheres with isolated cobalt single atomic sites: Superior electrocatalysts for oxygen reduction. J. Am. Chem. Soc. 2017, 139, 17269-17272.
[69]
Zhang, M. L.; Wang, Y. G.; Chen, W. X.; Dong, J. C.; Zheng, L. R.; Luo, J.; Wan, J. W.; Tian, S. B.; Cheong, W. C.; Wang, D. S. et al. Metal (hydr)oxides@polymer core-shell strategy to metal single-atom materials. J. Am. Chem. Soc. 2017, 139, 10976-10979.
[70]
Zhang, L. Z.; Jia, Y.; Liu, H. L.; Zhuang, L. Z.; Yan, X. C.; Lang, C. G.; Wang, X.; Yang, D. J.; Huang, K. K.; Feng, S. H. et al. Charge polarization from atomic metals on adjacent graphitic layers for enhancing the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2019, 58, 9404-9408.
[71]
Lin, J.; Wang, A. Q.; Qiao, B. T.; Liu, X. Y.; Yang, X. F.; Wang, X. D.; Liang, J. X.; Li, J.; Liu, J. Y.; Zhang, T. Remarkable performance of Ir1/FeOx single-atom catalyst in water gas shift reaction. J. Am. Chem. Soc. 2013, 135, 15314-15317.
[72]
Liu, P. X.; Zhao, Y.; Qin, R. X.; Mo, S. G.; Chen, G. X.; Gu, L.; Chevrier, D. M.; Zhang, P.; Guo, Q.; Zang, D. D. et al. Photochemical route for synthesizing atomically dispersed palladium catalysts. Science 2016, 352, 797-801.
[73]
Wan, J. W.; Chen, W. X.; Jia, C. Y.; Zheng, L. R.; Dong, J. C.; Zheng, X. S.; Wang, Y.; Yan, W. S.; Chen, C.; Peng, Q. et al. Defect effects on TiO2 nanosheets: Stabilizing single atomic site Au and promoting catalytic properties. Adv. Mater. 2018, 30, 1705369.
[74]
Chen, Y. J.; Ji, S. F.; Sun, W. M.; Chen, W. X.; Dong, J. C.; Wen, J. F.; Zhang, J.; Li, Z.; Zheng, L. R.; Chen, C. et al. Discovering partially charged single-atom Pt for enhanced anti-Markovnikov alkene hydrosilylation. J. Am. Chem. Soc. 2018, 140, 7407-7410.
[75]
Chen, Y. J.; Ji, S. F.; Sun, W. M.; Lei, Y. P.; Wang, Q. C.; Li, A.; Chen, W. X.; Zhou, G.; Zhang, Z. D.; Wang, Y. et al. Engineering the atomic interface with single platinum atoms for enhanced photocatalytic hydrogen production. Angew. Chem., Int. Ed. 2020, 59, 1295-1301.
[76]
Tang, Y.; Asokan, C.; Xu, M. J.; Graham, G. W.; Pan, X. Q.; Christopher, P.; Li, J.; Sautet, P. Rh single atoms on TiO2 dynamically respond to reaction conditions by adapting their site. Nat. Commun. 2019, 10, 4488.
[77]
Ren, Y. J.; Tang, Y.; Zhang, L. L.; Liu, X. Y.; Li, L.; Miao, S.; Sheng Su, D.; Wang, A. Q.; Li, J.; Zhang, T. Unraveling the coordination structure-performance relationship in Pt1/Fe2O3 single-atom catalyst. Nat. Commun. 2019, 10, 4500.
[78]
Park, J.; Lee, S.; Kim, H. E.; Cho, A.; Kim, S.; Ye, Y. J.; Han, J. W.; Lee, H.; Jang, J. H.; Lee, J. Investigation of the support effect in atomically dispersed Pt on WO3-x for utilization of Pt in the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2019, 58, 16038-16042.
[79]
Ma, Y. F.; Chi, B. L.; Liu, W.; Cao, L.; Lin, Y.; Zhang, X. H.; Ye, X. X.; Wei, S. Q.; Lu, J. L. Tailoring of the proximity of platinum single atoms on CeO2 using phosphorus boosts the hydrogenation activity. ACS Catal. 2019, 9, 8404-8412.
[80]
Ye, X. X.; Wang, H. W.; Lin, Y.; Liu, X. Y.; Cao, L.; Gu, J.; Lu, J. L. Insight of the stability and activity of platinum single atoms on ceria. Nano Res. 2019, 12, 1401-1409.
[81]
Chen, F.; Li, T. B.; Pan, X. L.; Guo, Y. L.; Han, B.; Liu, F.; Qiao, B. T.; Wang, A. Q.; Zhang, T. Pd1/CeO2 single-atom catalyst for alkoxycarbonylation of aryl iodides. Sci. China Mater., in press, .
[82]
Liu, K. L.; Qin, R. X.; Zhou, L. Y.; Liu, P. X.; Zhang, Q. H.; Jing, W. T.; Ruan, P. P.; Gu, L.; Fu, G.; Zheng, N. F. Cu2O-supported atomically dispersed Pd catalysts for semihydrogenation of terminal alkynes: Critical role of oxide supports. CCS Chem. 2019, 1, 207-214.
[83]
Zhou, X.; Shen, Q.; Yuan, K. D.; Yang, W. S.; Chen, Q. W.; Geng, Z. H.; Zhang, J. L.; Shao, X.; Chen, W.; Xu, G. Q. et al. Unraveling charge State of supported Au single-atoms during CO oxidation. J. Am. Chem. Soc. 2018, 140, 554-557.
[84]
Li, J. J.; Guan, Q. Q.; Wu, H.; Liu, W.; Lin, Y.; Sun, Z. H.; Ye, X. X.; Zheng, X. S.; Pan, H. B.; Zhu, J. F. et al. Highly active and stable metal single-atom catalysts achieved by strong electronic metal-support interactions. J. Am. Chem. Soc. 2019, 141, 14515-14519.
[85]
Zhang, J.; Wu, X.; Cheong, W. C.; Chen, W. X.; Lin, R.; Li, J.; Zheng, L. R.; Yan, W. S.; Gu, L.; Chen, C. et al. Cation vacancy stabilization of single-atomic-site Pt1/Ni(OH)x catalyst for diboration of alkynes and alkenes. Nat. Commun. 2018, 9, 1002.
[86]
Wang, F. F.; Li, Q.; Xu, D. S. Recent progress in semiconductor-based nanocomposite photocatalysts for solar-to-chemical energy conversion. Adv. Energy Mater. 2017, 7, 1700529.
[87]
Chandrasekaran, S.; Yao, L.; Deng, L. B.; Bowen, C.; Zhang, Y.; Chen, S. M.; Lin, Z. Q.; Peng, F.; Zhang, P. X. Recent advances in metal sulfides: From controlled fabrication to electrocatalytic, photocatalytic and photoelectrochemical water splitting and beyond. Chem. Soc. Rev. 2019, 48, 4178-4280.
[88]
Wang, B.; Cai, H. R.; Shen, S. H. Single metal atom photocatalysis. Small Methods 2019, 3, 1800447.
[89]
Liu, L. C.; Corma, A. Metal catalysts for heterogeneous catalysis: From single atoms to nanoclusters and nanoparticles. Chem. Rev. 2018, 118, 4981-5079.
[90]
Li, H. S.; Wang, S. S.; Sawada, H.; Han, G. G. D.; Samuels, T.; Allen, C. S.; Kirkland, A. I.; Grossman, J. C.; Warner, J. H. Atomic structure and dynamics of single platinum atom interactions with monolayer MoS2. ACS Nano 2017, 11, 3392-3403.
[91]
Liu, G. L.; Robertson, A. W.; Li, M. M. J.; Kuo, W. C. H.; Darby, M. T.; Muhieddine, M. H.; Lin, Y. C.; Suenaga, K.; Stamatakis, M.; Warner, J. H. et al. MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction. Nat. Chem. 2017, 9, 810-816.
[92]
Liu, J.; Zhao, Q.; Liu, J. L.; Wu, Y. S.; Cheng, Y.; Ji, M. W.; Qian, H. M.; Hao, W. C.; Zhang, L. J.; Wei, X. J. et al. Heterovalent-doping-enabled efficient dopant luminescence and controllable electronic impurity via a new strategy of preparing II-VI nanocrystals. Adv. Mater. 2015, 27, 2753-2761.
[93]
Wang, H. Z.; Gao, Y. Y.; Liu, J.; Li, X. Y.; Ji, M. W.; Zhang, E. H.; Cheng, X. Y.; Xu, M.; Liu, J. J.; Rong, H. P. et al. Efficient plasmonic Au/CdSe nanodumbbell for photoelectrochemical hydrogen generation beyond visible region. Adv. Energy Mater. 2019, 9, 1803889.
[94]
Pan, R. R.; Liu, J.; Li, Y. M.; Li, X. Y.; Zhang, E. H.; Di, Q. M.; Su, M. Y.; Zhang, J. T. Electronic doping-enabled transition from n- to p-type conductivity over Au@CdS core-shell nanocrystals toward unassisted photoelectrochemical water splitting. J. Mater. Chem. A 2019, 7, 23038-23045.
[95]
Shen, R. G.; Chen, W. X.; Peng, Q.; Lu, S. Q.; Zheng, L. R.; Cao, X.; Wang, Y.; Zhu, W.; Zhang, J. T.; Zhuang, Z. B. et al. High-concentration single atomic Pt sites on hollow CuSx for selective O2 reduction to H2O2 in acid solution. Chem 2019, 5, 2099-2110.
[96]
Ge, J. J.; He, D. S.; Chen, W. X.; Ju, H. X.; Zhang, H.; Chao, T. T.; Wang, X. Q.; You, R.; Lin, Y.; Wang, Y. et al. Atomically dispersed Ru on ultrathin Pd nanoribbons. J. Am. Chem. Soc. 2016, 138, 13850-13853.
[97]
Zhang, H. J.; Watanabe, T.; Okumura, M.; Haruta, M.; Toshima, N. Catalytically highly active top gold atom on palladium nanocluster. Nat. Mater. 2012, 11, 49-52.
[98]
Pei, G. X.; Liu, X. Y.; Wang, A. Q.; Lee, A. F.; Isaacs, M. A.; Li, L.; Pan, X. L.; Yang, X. F.; Wang, X. D.; Tai, Z. J. et al. Ag alloyed Pd single-atom catalysts for efficient selective hydrogenation of acetylene to ethylene in excess ethylene. ACS Catal. 2015, 5, 3717-3725.
[99]
Mao, J. J.; He, C. T.; Pei, J. J.; Chen, W. X.; He, D. S.; He, Y. Q.; Zhuang, Z. B.; Chen, C.; Peng, Q.; Wang, D. S. et al. Accelerating water dissociation kinetics by isolating cobalt atoms into ruthenium lattice. Nat. Commun. 2018, 9, 4958.
[100]
Liu, J. L.; Lucci, F. R.; Yang, M.; Lee, S.; Marcinkowski, M. D.; Therrien, A. J.; Williams, C. T.; Sykes, E. C. H.; Flytzani-Stephanopoulos, M. Tackling CO poisoning with single-atom alloy catalysts. J. Am. Chem. Soc. 2016, 138, 6396-6399.
[101]
Yao, Y. C.; Hu, S. L.; Chen, W. X.; Huang, Z. Q.; Wei, W. C.; Yao, T.; Liu, R. R.; Zang, K. T.; Wang, X. Q.; Wu, G. et al. Engineering the electronic structure of single atom Ru sites via compressive strain boosts acidic water oxidation electrocatalysis. Nat. Catal. 2019, 2, 304-313.
[102]
Rong, H. P.; Mao, J. J.; Xin, P. Y.; He, D. S.; Chen, Y. J.; Wang, D. S.; Niu, Z. Q.; Wu, Y.; Li, Y. D. Kinetically controlling surface structure to construct defect-rich intermetallic nanocrystals: Effective and stable catalysts. Adv. Mater. 2016, 28, 2540-2546.
[103]
Wu, H. H.; Li, H. B.; Zhao, X. F.; Liu, Q. F.; Wang, J.; Xiao, J. P.; Xie, S. H.; Si, R.; Yang, F.; Miao, S. et al. Highly doped and exposed Cu(I)-N active sites within graphene towards efficient oxygen reduction for zinc-air batteries. Energy Environ. Sci. 2016, 9, 3736-3745.
[104]
Zhang, H. N.; Li, J.; Xi, S. B.; Du, Y. H.; Hai, X.; Wang, J. Y.; Xu, H. M.; Wu, G.; Zhang, J.; Lu, J. et al. A graphene-supported single-atom FeN5 catalytic site for efficient electrochemical CO2 reduction. Angew. Chem., Int. Ed. 2019, 58, 14871-14876.
[105]
Wang, X. Q.; Chen, Z.; Zhao, X. Y.; Yao, T.; Chen, W. X.; You, R.; Zhao, C. M.; Wu, G.; Wang, J.; Huang, W. X. et al. Regulation of coordination number over single Co sites: Triggering the efficient electroreduction of CO2. Angew. Chem., Int. Ed. 2018, 57, 1944-1948.
[106]
Pan, Y.; Chen, Y. J.; Wu, K. L.; Chen, Z.; Liu, S. J.; Cao, X.; Cheong, W. C.; Meng, T.; Luo, J.; Zheng, L. R. et al. Regulating the coordination structure of single-atom Fe-NxCy catalytic sites for benzene oxidation. Nat. Commun. 2019, 10, 4290.
[107]
Qu, Y. T.; Li, Z. J.; Chen, W. X.; Lin, Y.; Yuan, T. W.; Yang, Z. K.; Zhao, C. M.; Wang, J.; Zhao, C.; Wang, X. et al. Direct transformation of bulk copper into copper single sites via emitting and trapping of atoms. Nat. Catal. 2018, 1, 781-786.
[108]
Wei, S. J.; Li, A.; Liu, J. C.; Li, Z.; Chen, W. X.; Gong, Y.; Zhang, Q. H.; Cheong, W. C.; Wang, Y.; Zheng, L. R. et al. Direct observation of noble metal nanoparticles transforming to thermally stable single atoms. Nat. Nanotechnol. 2018, 13, 856-861.
[109]
Ke, J.; Zhu, W.; Jiang, Y. Y.; Si, R.; Wang, Y. J.; Li, S. C.; Jin, C. H.; Liu, H. C.; Song, W. G.; Yan, C. H. et al. Strong local coordination structure effects on subnanometer PtOx clusters over CeO2 nanowires probed by low-temperature CO oxidation. ACS Catal. 2015, 5, 5164-5173.
[110]
Nan, B.; Hu, X. C.; Wang, X.; Jia, C. J.; Ma, C.; Li, M. X.; Si, R. Effects of multiple platinum species on catalytic reactivity distinguished by electron microscopy and X-ray absorption spectroscopy techniques. J. Phys. Chem. C 2017, 121, 25805-25817.
[111]
Ren, Y. J.; Tang, Y.; Zhang, L. L.; Liu, X. Y.; Li, L.; Miao, S.; Su, D. S.; Wang, A. Q.; Li, J.; Zhang, T. Unraveling the coordination structure-performance relationship in Pt1/Fe2O3 single-atom catalyst. Nat. Commun. 2019, 10, 4500.
[112]
Ye, T. N.; Xiao, Z. W.; Li, J.; Gong, Y. T.; Abe, H.; Niwa, Y.; Sasase, M.; Kitano, M.; Hosono, H. Stable single platinum atoms trapped in sub-nanometer cavities in 12CaO·7Al2O3 for chemoselective hydrogenation of nitroarenes. Nat. Commun. 2020, 11, 1020.
[113]
Shen, G. Q.; Zhang, R. R.; Pan, L.; Hou, F.; Zhao, Y. J.; Shen, Z. Y.; Mi, W. B.; Shi, C. X.; Wang, Q. F.; Zhang, X. W. et al. Regulating the spin state of FeIII by atomically anchoring on ultrathin titanium dioxide for efficient oxygen evolution electrocatalysis. Angew. Chem., Int. Ed. 2020, 59, 2313-2317.
[114]
Zhao, G. F.; Yang, F.; Chen, Z. J.; Liu, Q. F.; Ji, Y. J.; Zhang, Y.; Niu, Z. Q.; Mao, J. J.; Bao, X. H.; Hu, P. J. et al. Metal/oxide interfacial effects on the selective oxidation of primary alcohols. Nat. Commun. 2017, 8, 14039.
[115]
Lei, Y.; Liu, B.; Lu, J. L.; Libera, J. A.; Greeley, J. P.; Elam, J. W. Effects of chlorine in titanium oxide on palladium atomic layer deposition. J. Phys. Chem. C 2014, 118, 22611-22619.
[116]
Yin, X.; Utetiwabo, W.; Sun, S. H.; Lian, Y. M.; Chen, R. J.; Yang, W. Incorporation of CeF3 on single-atom dispersed Fe/N/C with oxophilic interface as highly durable electrocatalyst for proton exchange membrane fuel cell. J. Catal. 2019, 374, 43-50.
[117]
Wang, J.; Huang, Z. Q.; Liu, W.; Chang, C. R.; Tang, H. L.; Li, Z. J.; Chen, W. X.; Jia, C. J.; Yao, T.; Wei, S. Q. et al. Design of N-coordinated dual-metal sites: A stable and active Pt-free catalyst for acidic oxygen reduction reaction. J. Am. Chem. Soc. 2017, 139, 17281-17284.
[118]
Lu, Z. Y.; Wang, B.; Hu, Y. F.; Liu, W.; Zhao, Y. F.; Yang, R. O.; Li, Z. P.; Luo, J.; Chi, B.; Jiang, Z. et al. An isolated zinc-cobalt atomic pair for highly active and durable oxygen reduction. Angew. Chem., Int. Ed. 2019, 58, 2622-2626.
[119]
Zhang, L.; Si, R. T.; Liu, H. S.; Chen, N.; Wang, Q.; Adair, K.; Wang, Z. Q.; Chen, J. T.; Song, Z. X.; Li, J. J. et al. Atomic layer deposited Pt-Ru dual-metal dimers and identifying their active sites for hydrogen evolution reaction. Nat. Commun. 2019, 10, 4936.
[120]
Bai, L. C.; Hsu, C. S.; Alexander, D. T. L.; Chen, H. M.; Hu, X. L. A cobalt-iron double-atom catalyst for the oxygen evolution reaction. J. Am. Chem. Soc. 2019, 141, 14190-14199.
[121]
Nguyen, L.; Zhang, S. R.; Tan, L.; Tang, Y.; Liu, J. Y.; Tao, F. F. Ir1Znn bimetallic site for efficient production of hydrogen from methanol. ACS Sustainable Chem. Eng. 2019, 7, 18793-18800.
[122]
Han, X. P.; Ling, X. F.; Yu, D. S.; Xie, D. Y.; Li, L. L.; Peng, S. J.; Zhong, C.; Zhao, N. Q.; Deng, Y. D.; Hu, W. B. Atomically dispersed binary Co-Ni sites in nitrogen-doped hollow carbon nanocubes for reversible oxygen reduction and evolution. Adv. Mater. 2019, 31, 1905622.
[123]
Wu, K. L.; Chen, X.; Liu, S. J.; Pan, Y.; Cheong, W. C.; Zhu, W.; Cao, X.; Shen, R. G.; Chen, W. X.; Luo, J. et al. Porphyrin-like Fe-N4 sites with sulfur adjustment on hierarchical porous carbon for different rate-determining steps in oxygen reduction reaction. Nano Res. 2018, 11, 6260-6269.
[124]
Mun, Y.; Lee, S.; Kim, K.; Kim, S.; Lee, S.; Han, J. W.; Lee, J. Versatile strategy for tuning ORR activity of a single Fe-N4 site by controlling electron-withdrawing/donating properties of a carbon plane. J. Am. Chem. Soc. 2019, 141, 6254-6262.
[125]
Chen, Y. J.; Ji, S. F.; Zhao, S.; Chen, W. X.; Dong, J. C.; Cheong, W. C.; Shen, R. A.; Wen, X. D.; Zheng, L. R.; Rykov, A. I. et al. Enhanced oxygen reduction with single-atomic-site iron catalysts for a zinc-air battery and hydrogen-air fuel cell. Nat. Commun. 2018, 9, 5422.
Publication history
Copyright
Acknowledgements

Publication history

Received: 18 January 2020
Revised: 10 March 2020
Accepted: 11 March 2020
Published: 30 March 2020
Issue date: July 2020

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020

Acknowledgements

This work was supported by the National Key R&D Program of China (Nos. 2018YFA0702003 and 2016YFA0202801), the National Natural Science Foundation of China (Nos. 51631001, 51872030, 21890383, 21671117, 21871159, 21901135, 51702016, and 51501010), Beijing Institute of Technology Research Fund Program for Young Scholars, and Beijing Municipal Science & Technology Commission (No. Z191100007219003).

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