单原子催化剂电子结构调控实现高效多相催化

doi:10.3866/PKU.WHXB202212020

摘要/Abstract

摘要：

过去十年见证了单原子催化领域的快速发展，其最高的原子利用效率和充分暴露的活性位点使得单原子催化剂对众多反应的催化活性具有显著提升。在单原子催化领域的早期发展阶段，研究者只是关注单原子催化剂催化活性与催化选择性的提高，而其内在的反应机理以及活性位点同催化性能之间的构效关系往往被忽视。关于单原子催化剂中金属-基底相互作用的深入探讨能够帮助我们理解催化机理，并进一步指导多相催化剂的理性设计。值得注意的是，由于单原子催化剂均一的活性位点及其几何构型，我们可以通过理论计算以及一些原位的表征技术，来揭示其中的金属-基底相互作用，继而进一步促进单原子催化领域的发展以及多相催化剂的理性设计。这篇综述总结了金属-基底相互作用的基本概念，其作用，以及其在一些重要多相催化中的应用，最后提出了金属-基底相互作用在单原子催化领域所面临的挑战与机遇。

关键词: 单原子催化剂, 金属-基底电子相互作用, 电子结构, 多相催化, 构效关系

Abstract:

Past decades have witnessed the flourish of single atom catalysts (SACs) owing to their high atom-utilization efficiency and completely exposed active sites, which endows SACs with remarkably enhanced catalytic activities for various reactions. In the early development stage of SACs, researchers focus on the improvement of the catalytic performance of the catalysts, whereas the intrinsic catalytic reaction mechanism and the relationship between the electronic states of the metal sites and catalytic performance are usually ignored. Moreover, some sophisticated and complex structures, such as dual-atom SACs, heteroatomic doped SACs, SACs with precise second coordination shell, and other synergetic catalysts containing SACs, were fabricated recently. The insight into electronic metal-support interaction (EMSI) aids the understanding of the catalytic mechanism and thus serves as a guide for the fabrication of heterogeneous catalysts. Notably, the uniform active sites and characteristic local coordination configuration of SACs provide excellent platforms to study EMSI and bridge the gap between homogeneous and heterogeneous catalysts, which will contribute to the understanding of structure-performance relationships and enhance the development of SACs and rational design of heterogeneous catalysts. EMSI is especially important in heterogeneous catalysis. Through the rational design of the local coordination environment of SACs, the electronic structure of active sites can be accurately regulated, which will shift their d-band centers. This significantly alters the adsorption capability of intermediates and influences the final catalytic performance of the catalysts. With the development of advanced operando characterization techniques, the evolution of configuration, electronic properties, and local coordination environment could be revealed, thus providing researchers with a clear picture of the intrinsic mechanism of the catalytic system. In addition, with the aid of theoretical calculations, catalyst screening will be considerably more convenient, which will significantly reduce the number of aimless trials. After the optimal structure is determined, researchers should devise precise fabrication methods to realize the configuration. Herein, we initially introduce the basic principles and effects of EMSI. The stabilization, electronic property regulation, and electron transfer tunneling effects of EMSI are the foundation of SACs synthesis and catalytic mechanism elucidation, of which the former requires strong coordination stabilization energies while the latter focuses on the electronic state evolution of the active sites. Subsequently, EMSI applications in several important heterogeneous catalysis processes, such as selective hydrogenation, alcohol oxidation, water-gas shift reaction, and hydroformylation, are reviewed. Finally, the review discusses the challenges and future prospects for the future development of EMSI on SACs.

Key words: Single atom catalysts, Electronic metal-support interaction, Electronic structure, Heterogeneous catalysis, Structure-performance relationship

罗耀武, 王定胜. 单原子催化剂电子结构调控实现高效多相催化[J]. 物理化学学报, 2023, 39(9), 2212020. doi: 10.3866/PKU.WHXB202212020

Yaowu Luo, Dingsheng Wang. Enhancing Heterogeneous Catalysis by Electronic Property Regulation of Single Atom Catalysts[J]. Acta Phys. -Chim. Sin. 2023, 39(9), 2212020. doi: 10.3866/PKU.WHXB202212020

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202212020

https://www.whxb.pku.edu.cn/CN/Y2023/V39/I9/2212020

图/表 11

Fig 1

Fig 2

Fig 3

Fig 4

Fig 5

Fig 6

Fig 7

Fig 8

Fig 9

Fig 10

Scheme 1

参考文献 143

1	Fechete, I.; Wang, Y.; Védrine, J. C. Catal. Today 2012, 189, 2. doi: 10.1016/j.cattod.2012.04.003
2	Kumar, A.; Daw, P.; Milstein, D. Chem. Rev. 2022, 122, 385. doi: 10.1021/acs.chemrev.1c00412
3	Bai, S. T.; De Smet, G.; Liao, Y.; Sun, R.; Zhou, C.; Beller, M.; Maes, B. U. W.; Sels, B. F. Chem. Soc. Rev. 2021, 50, 4259. doi: 10.1039/d0cs01331e
4	Yang, X.; Wang, A.; Qiao, B.; Li, J.; Liu, J.; Zhang, T. Acc. Chem. Res. 2013, 46, 1740. doi: 10.1021/ar300361m
5	Li, Z.; Ji, S.; Liu, Y.; Cao, X.; Tian, S.; Chen, Y.; Niu, Z.; Li, Y. Chem. Rev. 2020, 120, 623. doi: 10.1021/acs.chemrev.9b00311
6	Cui, X.; Li, W.; Ryabchuk, P.; Junge, K.; Beller, M. Nat. Catal. 2018, 1, 385. doi: 10.1038/s41929-018-0090-9
7	Qiao, B.; Wang, A.; Yang, X.; Allard, L. F.; Jiang, Z.; Cui, Y.; Liu, J.; Li, J.; Zhang, T. Nat. Chem. 2011, 3, 634. doi: 10.1038/nchem.1095
8	Cui, T.; Wang, Y. P.; Ye, T.; Wu, J.; Chen, Z.; Li, J.; Lei, Y.; Wang, D.; Li, Y. Angew. Chem. Int. Ed. 2022, 61, e202115219. doi: 10.1002/anie.202115219
9	Zhang, N.; Zhang, X.; Kang, Y.; Ye, C.; Jin, R.; Yan, H.; Lin, R.; Yang, J.; Xu, Q.; Wang, Y.; et al. Angew. Chem. Int. Ed. 2021, 60, 13388. doi: 10.1002/anie.202101559
10	Wang, B.; Cheng, C.; Jin, M.; He, J.; Zhang, H.; Ren, W.; Li, J.; Wang, D.; Li, Y. Angew. Chem. Int. Ed. 2022, 61, e202207268. doi: 10.1002/anie.202207268
11	Li, W. H.; Yang, J.; Wang, D. Angew. Chem. Int. Ed. 2022, e202213318. doi: 10.1002/anie.202213318
12	Zheng, X.; Li, B.; Wang, Q.; Wang, D.; Li, Y. Nano Res. 2022, 15, 7806. doi: 10.1007/s12274-022-4429-9
13	Zhang, Z.; Zhang, L.; Wang, X.; Feng, Y.; Liu, X.; Sun, W. Nano Res. 2022, 16, 343. doi: 10.1007/s12274-022-4823-3
14	Shen, Q.; Jin, H.; Li, P.; Yu, X.; Zheng, L.; Song, W.; Cao, C. Nano Res. 2022, 15, 5024. doi: 10.1007/s12274-022-4235-4
15	Liu, Z.; Du, Y.; Yu, R.; Zheng, M.; Hu, R.; Wu, J.; Xia, Y.; Zhuang, Z.; Wang, D. Angew. Chem. Int. Ed. 2022, 62, e202212653. doi: 10.1002/anie.202212653
16	Zhuang, Z.; Xia, L.; Huang, J.; Zhu, P.; Li, Y.; Ye, C.; Xia, M.; Yu, R.; Lang, Z.; Zhu, J.; et al. Angew. Chem. Int. Ed. 2022, e202212335. doi: 10.1002/anie.202212335
17	Zhu, P.; Xiong, X.; Wang, D. Nano Res. 2022, 15, 5792. doi: 10.1007/s12274-022-4265-y
18	Wang, Y.; Zheng, X.; Wang, D. Nano Res. 2021, 15, 1730. doi: 10.1007/s12274-021-3794-0
19	Hu, P.; Huang, Z.; Amghouz, Z.; Makkee, M.; Xu, F.; Kapteijn, F.; Dikhtiarenko, A.; Chen, Y.; Gu, X.; Tang, X. Angew. Chem. Int. Ed. 2014, 53, 3418. doi: 10.1002/anie.201309248
20	Li, R.; Wang, D. Nano Res. 2022, 15, 6888. doi: 10.1007/s12274-022-4371-x
21	Li, Z.; Liu, F.; Jiang, Y.; Ni, P.; Zhang, C.; Wang, B.; Chen, C.; Lu, Y. Nano Res. 2022, 15, 4411. doi: 10.1007/s12274-021-4029-0
22	Jiang, B.; Guo, Z.; Liang, M. Nano Res. 2022, doi: 10.1007/s12274-022-4856-7
23	S. J. Tauster; Fung, S. C.; Garten, R. L. J. Am. Chem. Soc. 1978, 100, 170. doi: 10.1021/ja00469a029
24	Bruix, A.; Rodriguez, J. A.; Ramirez, P. J.; Senanayake, S. D.; Evans, J.; Park, J. B.; Stacchiola, D.; Liu, P.; Hrbek, J.; Illas, F. J. Am. Chem. Soc. 2012, 134, 8968. doi: 10.1021/ja302070k
25	Campbell, C. T. Nat. Chem. 2012, 4, 597. doi: 10.1038/nchem.1412
26	Uzun, A.; Ortalan, V.; Browning, N. D.; Gates, B. C. J. Catal. 2010, 269, 318. doi: 10.1016/j.jcat.2009.11.017
27	Chen, Y.; Wang, L.; Yao, Z.; Hao, L.; Tan, X.; Masa, J.; Robertson, A. W.; Sun, Z. Acta Phys. -Chim. Sin. 2022, 38, 2207024.
	陈宇新, 王丽君, 姚志波, 郝磊端, 谭心怡, Masa, J., Robertson, A. W., 孙振宇. 物理化学学报, 2022, 38, 2207024. doi: 10.3866/PKU.WHXB202207024
28	Ji, S.; Chen, Y.; Wang, X.; Zhang, Z.; Wang, D.; Li, Y. Chem. Rev. 2020, 120, 11900. doi: 10.1021/acs.chemrev.9b00818
29	Liu, J. ACS Catal. 2016, 7, 34. doi: 10.1021/acscatal.6b01534
30	Chen, Y.; Ji, S.; Zhao, S.; Chen, W.; Dong, J.; Cheong, W. C.; Shen, R.; Wen, X.; Zheng, L.; Rykov, A. I.; et al. Nat. Commun. 2018, 9, 5422. doi: 10.1038/s41467-018-07850-2
31	Chen, Y.; Ji, S.; Wang, Y.; Dong, J.; Chen, W.; Li, Z.; Shen, R.; Zheng, L.; Zhuang, Z.; Wang, D.; et al. Angew. Chem. Int. Ed. 2017, 56, 6937. doi: 10.1002/anie.201702473
32	Wei, S.; Wang, Y.; Chen, W.; Li, Z.; Cheong, W. C.; Zhang, Q.; Gong, Y.; Gu, L.; Chen, C.; Wang, D.; et al. Chem. Sci. 2019, 11, 786. doi: 10.1039/c9sc05005
33	Chen, S.; Li, W. H.; Jiang, W.; Yang, J.; Zhu, J.; Wang, L.; Ou, H.; Zhuang, Z.; Chen, M.; Sun, X.; et al. Angew. Chem. Int. Ed. 2022, 61, e202114450. doi: 10.1002/anie.202114450
34	Zhang, E.; Tao, L.; An, J.; Zhang, J.; Meng, L.; Zheng, X.; Wang, Y.; Li, N.; Du, S.; Zhang, J.; et al. Angew. Chem. Int. Ed. 2022, 61, e202117347. doi: 10.1002/anie.202117347
35	Zhang, Z.; Zhu, J.; Chen, S.; Sun, W.; Wang, D. Angew. Chem. Int. Ed. 2022, 62, e202215136. doi: 10.1002/anie.202215136
36	Chen, Y.; Ji, S.; Sun, W.; Lei, Y.; Wang, Q.; Li, A.; Chen, W.; Zhou, G.; Zhang, Z.; Wang, Y.; et al. Angew. Chem. Int. Ed. 2020, 59, 1295. doi: 10.1002/anie.201912439
37	Fan, Q.; Gao, P.; Ren, S.; Qu, Y.; Kong, C.; Yang, J.; Wu, Y. Nano Res. 2022, doi: 10.1007/s12274-022-4472-6
38	hang, N.; Zhang, X.; Tao, L.; Jiang, P.; Ye, C.; Lin, R.; Huang, Z.; Li, A.; Pang, D.; Yan, H.; et al. Angew. Chem. Int. Ed. 2021, 60, 6170. doi: 10.1002/anie.202014718
39	Qu, Y.; Li, Z.; Chen, W.; Lin, Y.; Yuan, T.; Yang, Z.; Zhao, C.; Wang, J.; Zhao, C.; Wang, X.; et al. > Nat. Catal. 2018, 1, 781. doi: 10.1038/s41929-018-0146-x
40	Moliner, M.; Gabay, J. E.; Kliewer, C. E.; Carr, R. T.; Guzman, J.; Casty, G. L.; Serna, P.; Corma, A. J. Am. Chem. Soc. 2016, 138, 15743. doi: 10.1021/jacs.6b10169
41	Gao, C.; Low, J.; Long, R.; Kong, T.; Zhu, J.; Xiong, Y. Chem. Rev. 2020, 120, 12175. doi: 10.1021/acs.chemrev.9b00840
42	Cui, X.; Wang, J.; Liu, B.; Ling, S.; Long, R.; Xiong, Y. J. Am. Chem. Soc. 2018, 140, 16514. doi: 10.1021/jacs.8b06723
43	Frenkel, A. I. Chem. Soc. Rev. 2012, 41, 8163. doi: 10.1039/c2cs35174a
44	Hall, E. R.; Pollock, C. J.; Bendix, J.; Collins, T. J.; Glatzel, P.; DeBeer, S. J. Am. Chem. Soc. 2014, 136, 10076. doi: 10.1021/ja504206y
45	Ding, K.; Gulec, A.; Johnson, A. M.; Schweitzer, N. M.; Stucky, G. D.; Marks, L. D.; Stair, P. C. Science 2015, 350, 189. doi: 10.1126/science.aac6368
46	Gu, Y.; Xi, B. J.; Zhang, H.; Ma, Y. C.; Xiong, S. L. Angew. Chem. Int. Ed. 2022, 61, e202202200. doi: 10.1002/anie.202202200
47	Yang, J.; Li, W.; Wang, D.; Li, Y. Adv. Mater. 2020, 32, e2003300. doi: 10.1002/adma.202003300
48	Zhang, J.; Zheng, C.; Zhang, M.; Qiu, Y.; Xu, Q.; Cheong, W. -C.; Chen, W.; Zheng, L.; Gu, L.; Hu, Z.; et al. Nano Res. 2020, 13, 3082. doi: 10.1007/s12274-020-2977-4
49	Huang, K.; Fu, H.; Shi, W.; Wang, H.; Cao, Y.; Yang, G.; Peng, F.; Wang, Q.; Liu, Z.; Zhang, B.; et al. J. Catal. 2019, 377, 283. doi: 10.1016/j.jcat.2019.06.047
50	Li, Z.; Fan, T.; Li, H.; Lu, X.; Ji, S.; Zhang, J.; Horton, J. H.; Xu, Q.; Zhu, J. Small 2022, 18, 2106614. doi: 10.1002/smll.202106614
51	Zhao, J.; Ji, S.; Guo, C.; Li, H.; Dong, J.; Guo, P.; Wang, D.; Li, Y.; Toste, F. D. Nat. Catal. 2021, 4, 523. doi: 10.1038/s41929-021-00637-7
52	Cao, T.; Lin, R.; Liu, S.; Cheong, W. -C. M.; Li, Z.; Wu, K.; Zhu, Y.; Wang, X.; Zhang, J.; Li, Q.; et al. Nano Res. 2022, 15, 3959. doi: 10.1007/s12274-022-4076-1
53	Li, W. H.; Ye, B. C.; Yang, J.; Wang, Y.; Yang, C. J.; Pan, Y. M.; Tang, H. T.; Wang, D.; Li, Y. Angew. Chem. Int. Ed. 2022, 61, e202209749. doi: 10.1002/anie.202209749
54	Xiong, Y.; Sun, W.; Han, Y.; Xin, P.; Zheng, X.; Yan, W.; Dong, J.; Zhang, J.; Wang, D.; Li, Y. Nano Res. 2021, 14, 2418. doi: 10.1007/s12274-020-3244-4
55	Yan, H.; Cheng, H.; Yi, H.; Lin, Y.; Yao, T.; Wang, C.; Li, J.; Wei, S.; Lu, J. J. Am. Chem. Soc. 2015, 137, 10484. doi: 10.1021/jacs.5b06485
56	Wang, G.; Chen, Z.; Wang, T.; Wang, D.; Mao, J. Angew. Chem. Int. Ed. 2022, e202210789. doi: 10.1002/anie.202210789
57	Sun, X.; Sun, L.; Li, G.; Tuo, Y.; Ye, C.; Yang, J.; Low, J.; Yu, X.; Bitter, J. H.; Lei, Y.; et al. Angew. Chem. Int. Ed. 2022, e202207677. doi: 10.1002/anie.202207677
58	Hu, B.; Huang, A.; Zhang, X.; Chen, Z.; Tu, R.; Zhu, W.; Zhuang, Z.; Chen, C.; Peng, Q.; Li, Y. Nano Res. 2021, 14, 3482. doi: 10.1007/s12274-021-3535-4
59	Peng, J.-X.; Yang, W.; Jia, Z.; Jiao, L.; Jiang, H.-L. Nano Res. 2022, 15, 10063. doi: 10.1007/s12274-022-4467-3
60	Chen, Y.; Gao, R.; Ji, S.; Li, H.; Tang, K.; Jiang, P.; Hu, H.; Zhang, Z.; Hao, H.; Qu, Q.; et al. Angew. Chem. Int. Ed. 2021, 60, 3212. doi: 10.1002/anie.202012798
61	Sun, X.; Tuo, Y.; Ye, C.; Chen, C.; Lu, Q.; Li, G.; Jiang, P.; Chen, S.; Zhu, P.; Ma, M.; et al. Angew. Chem. Int. Ed. 2021, 60, 23614. doi: 10.1002/anie.202110433
62	Liang, J.-X.; Lin, J.; Liu, J.; Wang, X.; Zhang, T.; Li, J. Angew. Chem. Int. Ed. 2020, 59, 12868. doi: 10.1002/anie.201914867
63	Liu, P.; Zhao, Y.; Qin, R.; Mo, S.; Chen, G.; Gu, L.; Chevrier, D. M.; Zhang, P.; Guo, Q.; Zang, D.; et al. Science 2016, 352, 797. doi: 10.1126/science.aaf5251
64	Li, Z.; Zhang, M.; Zhang, L.; Dong, X.; Leng, L.; Horton, J. H.; Wang, J. Nano Res. 2022, 15, 1338. doi: 10.1007/s12274-021-3662-y
65	Hou, Z.; Dai, L.; Deng, J.; Zhao, G.; Jing, L.; Wang, Y.; Yu, X.; Gao, R.; Tian, X.; Dai, H.; et al. Angew. Chem. Int. Ed. 2022, 61, e202201655. doi: 10.1002/anie.202201655
66	Xiao, K.; Lin, R.-T.; Wei, J.-X.; Li, N.; Li, H.; Ma, T.; Liu, Z.-Q. Nano Res. 2022, 15, 4980. doi: 10.1007/s12274-022-4140-x
67	Zhou, X. Acta Phys. -Chim. Sin. 2020, 37, 2008064.
	周雪梅. 物理化学学报, 2020, 37, 2008064. doi: 10.3866/PKU.WHXB202008064
68	Lin, L.; Wei, F.; Jiang, R.; Huang, Y.; Lin, S. Nano Res. 2022, 16, 309. doi: 10.1007/s12274-022-4800-x
69	Lin, L.; Zhou, W.; Gao, R.; Yao, S.; Zhang, X.; Xu, W.; Zheng, S.; Jiang, Z.; Yu, Q.; Li, Y. W.; et al. Nature 2017, 544, 80. doi: 10.1038/nature21672
70	Zhang, X.; Zhang, M.; Deng, Y.; Xu, M.; Artiglia, L.; Wen, W.; Gao, R.; Chen, B.; Yao, S.; Zhang, X.; et al. Nature 2021, 589, 396. doi: 10.1038/s41586-020-03130-6
71	Yang, J.; Li, W. H.; Tan, S.; Xu, K.; Wang, Y.; Wang, D.; Li, Y. Angew. Chem. Int. Ed. 2021, 60, 19085. doi: 10.1002/anie.202107123
72	Yang, S.; Kim, J.; Tak, Y. J.; Soon, A.; Lee, H. Angew. Chem. Int. Ed. 2016, 55, 2058. doi: 10.1002/anie.201509241
73	Sun, X.; Chen, C.; Xiong, C.; Zhang, C.; Zheng, X.; Wang, J.; Gao, X.; Yu, Z.-Q.; Wu, Y. Nano Res. 2022, 16, 917. doi: 10.1007/s12274-022-4802-8
74	Lin, J.; Wang, A.; Qiao, B.; Liu, X.; Yang, X.; Wang, X.; Liang, J.; Li, J.; Liu, J.; Zhang, T. J. Am. Chem. Soc. 2013, 135, 15314. doi: 10.1021/ja408574m
75	Mao, J.; He, C. T.; Pei, J.; Chen, W.; He, D.; He, Y.; Zhuang, Z.; Chen, C.; Peng, Q.; Wang, D.; et al. Nat. Commun. 2018, 9, 4958. doi: 10.1038/s41467-018-07288-6
76	an, A.; Wang, X.; Tang, K.; Zhang, Z.; Ye, C.; Kong, K.; Hu, H.; Zheng, L.; Jiang, P.; Zhao, C.; et al. Angew. Chem. Int. Ed. 2021, 60, 19262. doi: 10.1002/anie.202105186
77	Zheng, X.; Yang, J.; Xu, Z.; Wang, Q.; Wu, J.; Zhang, E.; Dou, S.; Sun, W.; Wang, D.; Li, Y. Angew. Chem. Int. Ed. 2022, 61, e202205946. doi: 10.1002/anie.202205946
78	Wang, Y.; Zheng, M.; Li, Y.; Ye, C.; Chen, J.; Ye, J.; Zhang, Q.; Li, J.; Zhou, Z.; Fu, X. Z.; et al. Angew. Chem. Int. Ed. 2022, 16, e202115735. doi: 10.1002/anie.202115735
79	Yang, W.; Zhao, X.; Wang, Y.; Wang, R.; Yang, W.; Peng, Y.; Li, J. Nano Res. 2022, 16, 219. doi: 10.1007/s12274-022-4690-y
80	Wei, S.; Li, A.; Liu, J. C.; Li, Z.; Chen, W.; Gong, Y.; Zhang, Q.; Cheong, W. C.; Wang, Y.; Zheng, L.; et al. Nat. Nanotechnol. 2018, 13, 856. doi: 10.1038/s41565-018-0197-9
81	Ruban, A.; Hammer, B.; Stoltze, P.; Skriver, H. L.; Nørskov, J. K. J. Mol. Catal. A: Chem. 1997, 115, 421. doi: 10.1016/S1381-1169(96)00348-2
82	Liu, S.; Li, Z.; Wang, C.; Tao, W.; Huang, M.; Zuo, M.; Yang, Y.; Yang, K.; Zhang, L.; Chen, S.; et al. Nat. Commun. 2020, 11, 938. doi: 10.1038/s41467-020-14565-w
83	Sun, L.; Xu, J.; Liu, X.; Qiao, B.; Li, L.; Ren, Y.; Wan, Q.; Lin, J.; Lin, S.; Wang, X.; et al. ACS Catal. 2021, 11, 5942. doi: 10.1021/acscatal.1c00231
84	Di, J.; Chen, C.; Yang, S. -Z.; Chen, S.; Duan, M.; Xiong, J.; Zhu, C.; Long, R.; Hao, W.; Chi, Z.; et al. Nat. Commun. 2019, 10, 2840. doi: 10.1038/s41467-019-10392-w
85	Meemken, F.; Baiker, A. Chem. Rev. 2017, 117, 11522. doi: 10.1021/acs.chemrev.7b00272
86	Zhang, L.; Zhou, M.; Wang, A.; Zhang, T. Chem. Rev. 2020, 120, 683. doi: 10.1021/acs.chemrev.9b00230
87	Li, Z.; Leng, L.; Lu, X.; Zhang, M.; Xu, Q.; Horton, J. H.; Zhu, J. Nano Res. 2022, 15, 3114. doi: 10.1007/s12274-021-4028-1
88	Studt, F.; Abild-Pedersen, F.; Bligaard, T.; Sørensen, R. Z.; Christensen, C. H.; Nørskov, J. K. Science 2008, 320, 1320. doi: 10.1126/science.1156660
89	Collins, B M. Selective Hydrogenation of Highly Unsaturated Hydrocarbons in The Presence of Less Unsaturated Hydrocarbons. US 4126645, 1978.
90	Vilé, G.; Albani, D.; Almora-Barrios, N.; López, N.; Pérez-Ramírez, J. ChemCatChem 2016, 8, 21. doi: 10.1002/cctc.201501269
91	Bridier, B.; Lopez, N.; Perez-Ramirez, J. Dalton Trans. 2010, 39, 8412. doi: 10.1039/c0dt00010h
92	McCue, A. J.; Guerrero-Ruiz, A.; Ramirez-Barria, C.; Rodríguez-Ramos, I.; Anderson, J. A. J. Catal. 2017, 355, 40. doi: 10.1016/j.jcat.2017.09.004
93	Pei, G. X.; Liu, X. Y.; Wang, A.; Lee, A. F.; Isaacs, M. A.; Li, L.; Pan, X.; Yang, X.; Wang, X.; Tai, Z.; et al. ACS Catal. 2015, 5, 3717. doi: 10.1021/acscatal.5b00700
94	Pei, G. X.; Liu, X. Y.; Wang, A.; Li, L.; Huang, Y.; Zhang, T.; Lee, J. W.; Jang, B. W. L.; Mou, C.-Y. New J. Chem. 2014, 38. doi: 10.1039/c3nj01136d
95	García-Mota, M.; Bridier, B.; Pérez-Ramírez, J.; López, N. J. Catal. 2010, 273, 92. doi: 10.1016/j.jcat.2010.04.018
96	Hamm, G.; Schmidt, T.; Breitbach, J.; Franke, D.; Becker, C.; Wandelt, K. Z. Phys. Chem. 2009, 223, 209. doi: 10.1524/zpch.2009.6033
97	Hu, M.; Wu, Z.; Yao, Z.; Young, J.; Luo, L.; Du, Y.; Wang, C.; Iqbal, Z.; Wang, X. J. Catal. 2021, 395, 46. doi: 10.1016/j.jcat.2020.12.009
98	Huang, F.; Deng, Y.; Chen, Y.; Cai, X.; Peng, M.; Jia, Z.; Ren, P.; Xiao, D.; Wen, X.; Wang, N.; et al. J. Am. Chem. Soc. 2018, 140, 13142. doi: 10.1021/jacs.8b07476
99	Huang, X.; Xia, Y.; Cao, Y.; Zheng, X.; Pan, H.; Zhu, J.; Ma, C.; Wang, H.; Li, J.; You, R.; et al. Nano Res. 2017, 10, 1302. doi: 10.1007/s12274-016-1416-z
100	Liu, Y.; Wang, B.; Fu, Q.; Liu, W.; Wang, Y.; Gu, L.; Wang, D.; Li, Y. Angew. Chem. Int. Ed. 2021, 60, 22522. doi: 10.1002/anie.202109538
101	Zhou, S.; Shang, L.; Zhao, Y.; Shi, R.; Waterhouse, G. I. N.; Huang, Y. C.; Zheng, L.; Zhang, T. Adv. Mater. 2019, 31, e1900509. doi: 10.1002/adma.201900509
102	Tew, M. W.; Janousch, M.; Huthwelker, T.; van Bokhoven, J. A. J. Catal. 2011, 283, 45. doi: 10.1016/j.jcat.2011.06.025
103	Lin, L.; Yao, S.; Gao, R.; Liang, X.; Yu, Q.; Deng, Y.; Liu, J.; Peng, M.; Jiang, Z.; Li, S.; et al. Nat. Nanotechnol. 2019, 14, 354. doi: 10.1038/s41565-019-0366-5
104	Blaser, H.-U.; Steiner, H.; Studer, M. ChemCatChem 2009, 1, 210. doi: 10.1002/cctc.200900129
105	Ma, Y.; Ren, Y.; Zhou, Y.; Liu, W.; Baaziz, W.; Ersen, O.; Pham-Huu, C.; Greiner, M.; Chu, W.; Wang, A.; et al. Angew. Chem. Int. Ed. 2020, 59, 21613. doi: 10.1002/anie.202007707
106	Liu, Y.; Zhang, W.; Zheng, Y.; Wu, K.; Dong, P.; He, R.; Lu, N.; Mao, J. Dalton Trans. 2021, 50, 7995. doi: 10.1039/d1dt01227d
107	Tian, S.; Hu, M.; Xu, Q.; Gong, W.; Chen, W.; Yang, J.; Zhu, Y.; Chen, C.; He, J.; Liu, Q.; et al. Sci. China Mater. 2021, 64, 642. doi: 10.1007/s40843-020-1443-8
108	Mäki-Arvela, P.; Hájek, J.; Salmi, T.; Murzin, D. Y. Appl. Catal. A-Gen. 2005, 292, 1. doi: 10.1016/j.apcata.2005.05.045
109	Lou, Y.; Zheng, Y.; Li, X.; Ta, N.; Xu, J.; Nie, Y.; Cho, K.; Liu, J. J. Am. Chem. Soc. 2019, 141, 19289. doi: 10.1021/jacs.9b06628
110	Feng, Y.; Long, S.; Chen, B.; Jia, W.; Xie, S.; Sun, Y.; Tang, X.; Yang, S.; Zeng, X.; Lin, L. ACS Catal. 2021, 11, 6398. doi: 10.1021/acscatal.1c01386
111	Gilkey, M. J.; Xu, B. ACS Catal. 2016, 6, 1420. doi: 10.1021/acscatal.5b02171
112	Ji, S.; Chen, Y.; Zhang, Z.; Cheong, W.-C.; Liu, Z.; Wang, D.; Li, Y. Nanoscale Horiz. 2019, 4, 902. doi: 10.1039/c9nh00036d
113	Liu, L.; Corma, A. Chem. Rev. 2018, 118, 4981. doi: 10.1021/acs.chemrev.7b00776
114	Jin, J.; Han, X.; Fang, Y.; Zhang, Z.; Li, Y.; Zhang, T.; Han, A.; Liu, J. Adv. Funct. Mater. 2022, 32, 2109218. doi: 10.1002/adfm.202109218
115	Li, T.; Liu, F.; Tang, Y.; Li, L.; Miao, S.; Su, Y.; Zhang, J.; Huang, J.; Sun, H.; Haruta, M.; et al. Angew. Chem. Int. Ed. 2018, 57, 7795. doi: 10.1002/anie.201803272
116	Lei, L.; Liu, H.; Wu, Z.; Qin, Z.; Wang, G.; Ma, J.; Luo, L.; Fan, W.; Wang, J. ACS Appl. Nano Mater. 2019, 2, 5214. doi: 10.1021/acsanm.9b01091
117	Xin, P.; Li, J.; Xiong, Y.; Wu, X.; Dong, J.; Chen, W.; Wang, Y.; Gu, L.; Luo, J.; Rong, H.; et al. Angew. Chem. Int. Ed. 2018, 57, 4642. doi: 10.1002/anie.201801103
118	Shang, Q.; Tang, N.; Qi, H.; Chen, S.; Xu, G.; Wu, C.; Pan, X.; Wang, X.; Cong, Y. Chin. J. Catal. 2020, 41, 1812. doi: 10.1016/s1872-2067(20)63651-8
119	Shang, Q.; Tang, N.; Qi, H.; Chen, S.; Xu, G.; Wu, C.; Pan, X.; Wang, X.; Cong, Y. J. Am. Chem. Soc. 2018, 140, 8652. doi: 10.1021/jacs.8b05107
120	Li, M.; Wu, S.; Yang, X.; Hu, J.; Peng, L.; Bai, L.; Huo, Q.; Guan, J. Appl. Catal. A-Gen. 2017, 543, 61. doi: 10.1016/j.apcata.2017.06.018
121	Xie, J.; Yin, K.; Serov, A.; Artyushkova, K.; Pham, H. N.; Sang, X.; Unocic, R. R.; Atanassov, P.; Datye, A. K.; Davis, R. J. ChemSusChem 2017, 10, 359. doi: 10.1002/cssc.201601364
122	Chen, Y.; Lin, J.; Wang, X. Chem. Commun. 2021, 58, 208. doi: 10.1039/d1cc04051k
123	Fu, Q.; Saltsburg, H.; Flytzani-Stephanopoulos, M. Science 2003, 301, 935. doi: 10.1126/science.1085721
124	Yang, M.; Li, S.; Wang, Y.; Herron, J. A.; Xu, Y.; Allard, L. F.; Lee, S.; Huang, J.; Mavrikakis, M.; Flytzani-Stephanopoulos, M. Science 2014, 346, 1498. doi: 10.1126/science.1260526
125	Zhai, Y.; Pierre, D.; Si, R.; Deng, W.; Ferrin, P.; Nilekar, A. U.; Peng, G.; Herron, J. A.; Bell, D. C.; Saltsburg, H.; et al. Science 2010, 329, 1633. doi: 10.1126/science.1192449
126	Chen, Y.; Lin, J.; Li, L.; Qjao, B.; Liu, J.; Su, Y.; Wang, X. ACS Catal. 2018, 8, 859. doi: 10.1021/acscatal.7b02751
127	Sun, X.; Lin, J.; Zhou, Y.; Li, L.; Su, Y.; Wang, X.; Zhang, T. AIChE J. 2017, 63, 4022. doi: 10.1002/aic.15759
128	Li, T.; Chen, F.; Lang, R.; Wang, H.; Su, Y.; Qiao, B.; Wang, A.; Zhang, T. Angew. Chem. Int. Ed. 2020, 59, 7430. doi: 10.1002/anie.202000998
129	Guan, H.; Lin, J.; Qiao, B.; Miao, S.; Wang, A.-Q.; Wang, X.; Zhang, T. AIChE J. 2017, 63, 2081. doi: 10.1002/aic.15585
130	Li, J.; Sun, L.; Wan, Q.; Lin, J.; Lin, S.; Wang, X. J. Phys. Chem. Lett. 2021, 12, 11415. doi: 10.1021/acs.jpclett.1c02762
131	Siyu Yao; Zhang, X.; Zhou, W.; Gao, R.; Xu, W.; Ye, Y.; Lin, L.; Wen, X.; Liu, P.; Chen, B.; et al. Science 2017, 357, 389. doi: 10.1126/science.aah4321
132	Dong, J.; Fu, Q.; Jiang, Z.; Mei, B.; Bao, X. J. Am. Chem. Soc. 2018, 140, 13808. doi: 10.1021/jacs.8b08246
133	Franke, R.; Selent, D.; Borner, A. Chem. Rev. 2012, 112, 5675. doi: 10.1021/cr3001803
134	Hanf, S.; Alvarado Rupflin, L.; Glaeser, R.; Schunk, S. A. Catalysts 2020, 10, 510. doi: 10.3390/catal10050510
135	Li, C.; Yan, L.; Lu, L.; Xiong, K.; Wang, W.; Jiang, M.; Liu, J.; Song, X.; Zhan, Z.; Jiang, Z.; et al. Green Chem. 2016, 18, 2995. doi: 10.1039/c6gc00728g
136	Sun, Q.; Dai, Z.; Liu, X.; Sheng, N.; Deng, F.; Meng, X.; Xiao, F. S. J. Am. Chem. Soc. 2015, 137, 5204. doi: 10.1021/jacs.5b02122
137	Zhao, K.; Wang, H.; Wang, X.; Li, T.; Dai, X.; Zhang, L.; Cui, X.; Shi, F. J. Catal. 2021, 401, 321. doi: 10.1016/j.jcat.2021.08.004
138	Li, C.; Sun, K.; Wang, W.; Yan, L.; Sun, X.; Wang, Y.; Xiong, K.; Zhan, Z.; Jiang, Z.; Ding, Y. J. Catal. 2017, 353, 123. doi: 10.1016/j.jcat.2017.07.022
139	Lang, R.; Li, T.; Matsumura, D.; Miao, S.; Ren, Y.; Cui, Y. -T.; Tan, Y.; Qiao, B.; Li, L.; Wang, A.; et al. Angew. Chem. Int. Ed. 2016, 55, 16054. doi: 10.1002/anie.201607885
140	Gao, P.; Liang, G.; Ru, T.; Liu, X.; Qi, H.; Wang, A.; Chen, F.-E. Nat. Commun. 2021, 12, 4698. doi: 10.1038/s41467-021-25061-0
141	Wang, L.; Zhang, W.; Wang, S.; Gao, Z.; Luo, Z.; Wang, X.; Zeng, R.; Li, A.; Li, H.; Wang, M.; et al. Nat. Commun. 2016, 7, 14036. doi: 10.1038/ncomms14036
142	Wei, B.; Liu, X.; Hua, K.; Deng, Y.; Wang, H.; Sun, Y. ACS Appl. Mater. Interfaces 2021, 13, 15113. doi: 10.1021/acsami.0c21749
143	Tang, P.; Paganelli, S.; Carraro, F.; Blanco, M.; Ricco, R.; Marega, C.; Badocco, D.; Pastore, P.; Doonan, C. J.; Agnoli, S. ACS Appl. Mater. Interfaces 2020, 12, 54798. doi: 10.1021/acsami.0c17073

[1]	朱锐杰, 康磊磊, 李林, 潘晓丽, 王华, 苏杨, 李广亿, 程鸿魁, 李仁贵, 刘晓艳, 王爱琴. WO₃-TiO₂负载的Pt单原子催化剂光热协同催化丙烷和丙烯氧化[J]. 物理化学学报, 2024, 40(1): 2303003 - .
[2]	Faizan Muhammad, 赵国琪, 张天旭, 王啸宇, 贺欣, 张立军. 空位有序双钙钛矿A₂BX₆的弹性和热电性质的第一性原理研究[J]. 物理化学学报, 2024, 40(1): 2303004 - .
[3]	宋千伟, 何观朝, 费慧龙. 基于单原子催化剂的光热催化转化：原理和应用[J]. 物理化学学报, 2023, 39(9): 2212038 -0 .
[4]	王晶晶, 曹贵强, 段瑞贤, 李向阳, 李喜飞. 金属单原子催化剂增强硫正极动力学的研究进展[J]. 物理化学学报, 2023, 39(5): 2212005 -0 .
[5]	唐甜蜜, 王振旅, 管景奇. 调控单位点M-N-C电催化剂的电子结构提升二氧化碳还原性能[J]. 物理化学学报, 2023, 39(4): 2208033 -0 .
[6]	刘真, 孟祥福, 古万苗, 查珺, 闫楠, 尤青, 夏楠, 王辉, 伍志鲲. 组合掺杂引入新型、多种镉配位方式增强金纳米团簇的电催化性能[J]. 物理化学学报, 2023, 39(12): 2212064 - .
[7]	郑书逸, 吴佳, 王可, 胡梦晨, 文欢, 尹诗斌. 钴掺杂电子调控Ni-Mo-O多孔纳米棒选择性氧化5-羟甲基糠醛耦合制氢[J]. 物理化学学报, 2023, 39(12): 2301032 - .
[8]	吴明亮, 章烨晖, 付战照, 吕之阳, 李强, 王金兰. 原子尺度钴基氮碳催化剂对析氧反应的构效关系的研究[J]. 物理化学学报, 2023, 39(1): 2207007 -0 .
[9]	马明军, 冯志超, 张小委, 孙超越, 王海青, 周伟家, 刘宏. 基于微生物作为智能模板的电催化剂制备与应用研究进展[J]. 物理化学学报, 2022, 38(6): 2106003 - .
[10]	陈宇新, 王丽君, 姚志波, 郝磊端, 谭心怡, Masa Justus, Robertson Alex W., 孙振宇. 单原子配位结构及与载体相互作用的调控用于二氧化碳电催化还原[J]. 物理化学学报, 2022, 38(11): 2207024 -0 .
[11]	周君慧, 敖志敏, 安太成. 基于密度泛函理论下H₂S在单原子催化剂V/Ti₂CO₂上的分解机理研究[J]. 物理化学学报, 2021, 37(8): 2007086 - .
[12]	陈鹏, 周莹, 董帆. 二维光催化材料电子结构和性能调控策略研究进展[J]. 物理化学学报, 2021, 37(8): 2010010 - .
[13]	周雪梅. 二氧化钛负载单原子催化剂用于光催化反应的研究[J]. 物理化学学报, 2021, 37(6): 2008064 - .
[14]	李亚文, 那广仁, 罗树林, 贺欣, 张立军. 全无机卤化铅钙钛矿的结构、热力学稳定性和电子性质[J]. 物理化学学报, 2021, 37(4): 2007015 - .
[15]	郑堂飞, 蒋金霞, 王健, 胡素芳, 丁炜, 魏子栋. 基于限域特性的电催化剂调控[J]. 物理化学学报, 2021, 37(11): 2011027 - .