Single-atom catalysis: a promising avenue for precisely controlling reaction pathways

Abstract

Single-atom catalysts (SACs), characterized by exceptionally high atom efficiency, have garnered significant attention across various catalytic reactions. Recent studies have showcased SACs with robust capabilities for precise catalysis, specifically targeting reactions along designated pathways. This review focuses on the advances in the precise activation and reconstruction of chemical bonds on SACs, including precise activation of C–O and C–H bonds and selective couplings involving C–C and C–N bonds. Our discussion begins with a thorough exploration of the factors that render SACs skilled in precise catalytic processes, encompassing the narrow d-band electronic state of single atom site resulting in the adsorption tendency, isolate site resulting in unique adsorption structure, and synergy effect of a single atom site with its neighbors. Subsequently, we elaborate on the applications of SACs in electrocatalysis and thermocatalysis including four prominent reactions, namely, electrochemical CO₂ reduction, urea electrochemical synthesis, CO₂ hydrogenation, and CH₄ activation. Then the concept of rational design of SACs for precisely controlling reaction pathways is discussed from the aspects of pore structure design, support-metal strong interaction, and support hydrophilic/hydrophobic. Finally, we summarize the challenges encountered by SACs in the field of precise catalytic processes and outline prospects for their further development in this domain.

Key words： single atom catalysts; selective oxidation; CO₂RR; bond coupling

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was financially supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB0600200), the National Key Research and Development Program of China (Grant No. 2021YFA1500502), the NSFC Center for Single-Atom Catalysis (Grant No. 22388102), the National Natural Science Foundation of China (Grant Nos. 22102176, U19A2015 and 21925803), CAS Project for Young Scientists in Basic Research (Grant Nos.YSBR-051, YSBR-022). The authors gratefully acknowledge the support of Photon Science Center for Carbon Neutrality.

References

1 Liu X , Dai L . Carbon-based metal-free catalysts. Nature Reviews. Materials, 2016, 1(11): 16064

2 Meirer F , Weckhuysen B M . Spatial and temporal exploration of heterogeneous catalysts with synchrotron radiation. Nature Reviews. Materials, 2018, 3(9): 324–340

3 Mitchell S , Pérez Ramírez J . Atomically precise control in the design of low-nuclearity supported metal catalysts. Nature Reviews. Materials, 2021, 6(11): 969–985

4 Zhao Z J , Liu S , Zha S , Cheng D , Studt F , Henkelman G , Gong J . Theory-guided design of catalytic materials using scaling relationships and reactivity descriptors. Nature Reviews. Materials, 2019, 4(12): 792–804

5 Suryanto B H R , Matuszek K , Choi J , Hodgetts R Y , Du H L , Bakker J M , Kang C S M , Cherepanov P V , Simonov A N , MacFarlane D R . Nitrogen reduction to ammonia at high efficiency and rates based on a phosphonium proton shuttle. Science, 2021, 372(6547): 1187–1191

6 Chen G F , Yuan Y , Jiang H , Ren S Y , Ding L X , Ma L , Wu T , Lu J , Wang H . Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper-molecular solid catalyst. Nature Energy, 2020, 5(8): 605–613

7 Chang F , Tezsevin I , de Rijk J W , Meeldijk J D , Hofmann J P , Er S , Ngene P , de Jongh P E . Potassium hydride-intercalated graphite as an efficient heterogeneous catalyst for ammonia synthesis. Nature Catalysis, 2022, 5(3): 222–230

8 Pan X , Jiao F , Miao D , Bao X . Oxide-zeolite-based composite catalyst concept that enables syngas chemistry beyond Fischer-Tropsch synthesis. Chemical Reviews, 2021, 121(11): 6588–6609

9 Rahmati M , Safdari M S , Fletcher T H , Argyle M D , Bartholomew C H . Chemical and thermal sintering of supported metals with emphasis on cobalt catalysts during Fischer-Tropsch synthesis. Chemical Reviews, 2020, 120(10): 4455–4533

10 Rommens K T , Saeys M . Molecular views on Fischer-Tropsch synthesis. Chemical Reviews, 2023, 123(9): 5798–5858

11 Service R F . Lithium-ion battery development takes nobel. Science, 2019, 366(6463): 292

12 Degen F , Winter M , Bendig D , Tübke J . Energy consumption of current and future production of lithium-ion and post lithium-ion battery cells. Nature Energy, 2023, 8(11): 1284–1295

13 Gent W E , Busse G M , House K Z . The predicted persistence of cobalt in lithium-ion batteries. Nature Energy, 2022, 7(12): 1132–1143

14 Feng X , Ren D , He X , Ouyang M . Mitigating thermal runaway of lithium-ion batteries. Joule, 2020, 4(4): 743–770

15 Harper G , Sommerville R , Kendrick E , Driscoll L , Slater P , Stolkin R , Walton A , Christensen P , Heidrich O , Lambert S . . Recycling lithium-ion batteries from electric vehicles. Nature, 2019, 575(7781): 75–86

16 Chen L D . Cations play an essential role in CO₂ reduction. Nature Catalysis, 2021, 4(8): 641–642

17 Yan B , Li Y , Cao W , Zeng Z , Liu P , Ke Z , Yang G . Highly efficient and highly selective CO₂ reduction to CO driven by laser. Joule, 2022, 6(12): 2735–2744

18 Kang W , Lee C C , Jasniewski A J , Ribbe M W , Hu Y . Structural evidence for a dynamic metallocofactor during N₂ reduction by Mo-nitrogenase. Science, 2020, 368(6497): 1381–1385

19 Weliwatte N S , Minteer S D . Photo-bioelectrocatalytic CO₂ reduction for a circular energy landscape. Joule, 2021, 5(10): 2564–2592

20 Yu X , Han P , Wei Z , Huang L , Gu Z , Peng S , Ma J , Zheng G . Boron-doped graphene for electrocatalytic N₂ reduction. Joule, 2018, 2(8): 1610–1622

21 Qing G , Ghazfar R , Jackowski S T , Habibzadeh F , Ashtiani M M , Chen C P , Smith M R III , Hamann T W . Recent advances and challenges of electrocatalytic N₂ reduction to ammonia. Chemical Reviews, 2020, 120(12): 5437–5516

22 Tanifuji K , Ohki Y . Metal-sulfur compounds in N₂ reduction and nitrogenase-related chemistry. Chemical Reviews, 2020, 120(12): 5194–5251

23 Stephens I E L , Rossmeisl J , Chorkendorff I . Toward sustainable fuel cells. Science, 2016, 354(6318): 1378–1379

24 Gittleman C S , Jia H , De Castro E S , Chisholm C R I , Kim Y S . Proton conductors for heavy-duty vehicle fuel cells. Joule, 2021, 5(7): 1660–1677

25 Zhou Z , Zhang Y , Shen Y , Liu S , Zhang Y . Molecular engineering of polymeric carbon nitride: advancing applications from photocatalysis to biosensing and more. Chemical Society Reviews, 2018, 47(7): 2298–2321

26 Feng Y , Long S , Tang X , Sun Y , Luque R , Zeng X , Lin L . Earth-abundant 3d-transition-metal catalysts for lignocellulosic biomass conversion. Chemical Society Reviews, 2021, 50(10): 6042–6093

27 Sudarsanam P , Peeters E , Makshina E V , Parvulescu V I , Sels B F . Advances in porous and nanoscale catalysts for viable biomass conversion. Chemical Society Reviews, 2019, 48(8): 2366–2421

28 Fang R , Dhakshinamoorthy A , Li Y , Garcia H . Metal organic frameworks for biomass conversion. Chemical Society Reviews, 2020, 49(11): 3638–3687

29 Rimer J D . Rational design of zeolite catalysts. Nature Catalysis, 2018, 1(7): 488–489

30 Xu D , Zhang S N , Chen J S , Li X H . Design of the synergistic rectifying interfaces in Mott-Schottky catalysts. Chemical Reviews, 2023, 123(1): 1–30

31 Durand D J , Fey N . Computational ligand descriptors for catalyst design. Chemical Reviews, 2019, 119(11): 6561–6594

32 Motagamwala A H , Dumesic J A . Microkinetic modeling: a tool for rational catalyst design. Chemical Reviews, 2021, 121(2): 1049–1076

33 Su D , Lam Z , Wang Y , Han F , Zhang M , Liu B , Chen H . Ultralong durability of ethanol oxidation reaction via morphological design. Joule, 2023, 7(11): 2568–2582

34 Wang L , Meng S , Tang C , Zhan C , Geng S , Jiang K , Huang X , Bu L . PtNi/PtIn-skin fishbone-like nanowires boost alkaline hydrogen oxidation catalysis. ACS Nano, 2023, 17(18): 17779–17789

35 Mehmood R , Fan W , Hu X , Li J , Liu P , Zhang Y , Zhou Z , Wang J , Liu M , Zhang F . Confirming high-valent iron as highly active species of water oxidation on the Fe, V-coupled bimetallic electrocatalyst: in situ analysis of X-ray absorption and mössbauer spectroscopy. Journal of the American Chemical Society, 2023, 145(22): 12206–12213

36 Das S , Pérez Ramírez J , Gong J , Dewangan N , Hidajat K , Gates B C , Kawi S . Core-shell structured catalysts for thermocatalytic, photocatalytic, and electrocatalytic conversion of CO₂. Chemical Society Reviews, 2020, 49(10): 2937–3004

37 Rideal E K . Prof. Paul Sabatier, For. Mem.R.S. Nature, 1941, 148(3750): 309

38 Tan T H , Xie B , Ng Y H , Abdullah S F B , Tang H Y M , Bedford N , Taylor R A , Aguey Zinsou K F , Amal R , Scott J . Unlocking the potential of the formate pathway in the photo-assisted sabatier reaction. Nature Catalysis, 2020, 3(12): 1034–1043

39 Hu S , Li W X . Sabatier principle of metal-support interaction for design of ultrastable metal nanocatalysts. Science, 2021, 374(6573): 1360–1365

40 Zhou Y , Wei F , Qi H , Chai Y , Cao L , Lin J , Wan Q , Liu X , Xing Y , Lin S . . Peripheral-nitrogen effects on the Ru₁ centre for highly efficient propane dehydrogenation. Nature Catalysis, 2022, 5(12): 1145–1156

41 Qiao B , Wang A , Yang X , Allard L F , Jiang Z , Cui Y , Liu J , Li J , Zhang T . Single-atom catalysis of CO oxidation using Pt₁/FeO_x. Nature Chemistry, 2011, 3(8): 634–641

42 Yang X F , Wang A , Qiao B , Li J , Liu J , Zhang T . Single-atom catalysts: a new frontier in heterogeneous catalysis. Accounts of Chemical Research, 2013, 46(8): 1740–1748

43 Liu L , Corma A . Metal catalysts for heterogeneous catalysis: from single atoms to nanoclusters and nanoparticles. Chemical Reviews, 2018, 118(10): 4981–5079

44 Zhang Y . Heterogeneous catalysis: single atoms on a roll. Nature Reviews Chemistry, 2018, 2(1): 0151

45 Wu X , Wang Q , Yang S , Zhang J , Cheng Y , Tang H , Ma L , Min X , Tang C , Jiang S P . . Sublayer-enhanced atomic sites of single atom catalysts through in situ atomization of metal oxide nanoparticles. Energy & Environmental Science, 2022, 15(3): 1183–1191

46 Jiang D , Wan G , Halldin Stenlid J , García Vargas C E , Zhang J , Sun C , Li J , Abild Pedersen F , Tassone C J , Wang Y . Dynamic and reversible transformations of subnanometre-sized palladium on ceria for efficient methane removal. Nature Catalysis, 2023, 6(7): 618–627

47 Agarwal N , Freakley S J , McVicker R U , Althahban S M , Dimitratos N , He Q , Morgan D J , Jenkins R L , Willock D J , Taylor S H . . Aqueous Au-Pd colloids catalyze selective CH₄ oxidation to CH₃OH with O₂ under mild conditions. Science, 2017, 358(6360): 223–227

48 Shoji S , Peng X , Yamaguchi A , Watanabe R , Fukuhara C , Cho Y , Yamamoto T , Matsumura S , Yu M W , Ishii S . . Photocatalytic uphill conversion of natural gas beyond the limitation of thermal reaction systems. Nature Catalysis, 2020, 3(2): 148–153

49 Xu S , Carter E A . Theoretical insights into heterogeneous (photo)electrochemical CO₂ reduction. Chemical Reviews, 2019, 119(11): 6631–6669

50 Rizo R , Arán Ais R M , Padgett E , Muller D A , Lázaro M J , Solla Gullón J , Feliu J M , Pastor E , Abruña H D . Pt-rich_core/Sn-rich_subsurface/Pt_skin nanocubes as highly active and stable electrocatalysts for the ethanol oxidation reaction. Journal of the American Chemical Society, 2018, 140(10): 3791–3797

51 Yang X , Liang Z , Chen S , Ma M , Wang Q , Tong X , Zhang Q , Ye J , Gu L , Yang N . A phosphorus-doped Ag@Pd catalyst for enhanced C–C bond cleavage during ethanol electrooxidation. Small, 2020, 16(47): 2004727

52 Vijay S , Ju W , Brückner S , Tsang S C , Strasser P , Chan K . Unified mechanistic understanding of CO₂ reduction to CO on transition metal and single atom catalysts. Nature Catalysis, 2021, 4(12): 1024–1031

53 Tang Y , Li Y , Fung V , Jiang D E , Huang W , Zhang S , Iwasawa Y , Sakata T , Nguyen L , Zhang X . . Single rhodium atoms anchored in micropores for efficient transformation of methane under mild conditions. Nature Communications, 2018, 9(1): 1231

54 Xie P , Ding J , Yao Z , Pu T , Zhang P , Huang Z , Wang C , Zhang J , Zecher Freeman N , Zong H . . Oxo dicopper anchored on carbon nitride for selective oxidation of methane. Nature Communications, 2022, 13(1): 1375

55 Wang Z , Liu S , Zhao X , Wang M , Zhang L , Qian T , Xiong J , Yang C , Yan C . Interfacial defect engineering triggered by single atom doping for highly efficient electrocatalytic nitrate reduction to ammonia. ACS Materials Letters, 2023, 5(4): 1018–1026

56 Ding J , Teng Z , Su X , Kato K , Liu Y , Xiao T , Liu W , Liu L , Zhang Q , Ren X . . Asymmetrically coordinated cobalt single atom on carbon nitride for highly selective photocatalytic oxidation of CH₄ to CH₃OH. Chem, 2023, 9(4): 1017–1035

57 Ding J , Wei Z , Li F , Zhang J , Zhang Q , Zhou J , Wang W , Liu Y , Zhang Z , Su X . . Atomic high-spin cobalt(II) center for highly selective electrochemical CO reduction to CH₃OH. Nature Communications, 2023, 14(1): 6550

58 Wang Q , Wang H , Cao H , Tung C W , Liu W , Hung S F , Wang W , Zhu C , Zhang Z , Cai W . . Atomic metal-non-metal catalytic pair drives efficient hydrogen oxidation catalysis in fuel cells. Nature Catalysis, 2023, 6(10): 916–926

59 Wang Y , Mao J , Meng X , Yu L , Deng D , Bao X . Catalysis with two-dimensional materials confining single atoms: concept, design, and applications. Chemical Reviews, 2019, 119(3): 1806–1854

60 NørskovJ KStoltzeP. Theoretical aspects of surface reactions. Surface Science, 1987, 189–190: 91–105

61 Greiner M T , Jones T E , Beeg S , Zwiener L , Scherzer M , Girgsdies F , Piccinin S , Armbrüster M , Knop Gericke A , Schlögl R . Free-atom-like d states in single-atom alloy catalysts. Nature Chemistry, 2018, 10(10): 1008–1015

62 Rosen A S , Vijay S , Persson K A . Free-atom-like d states beyond the dilute limit of single-atom alloys. Chemical Science, 2023, 14(6): 1503–1511

63 Spivey T D , Holewinski A . Selective interactions between free-atom-like d-states in single-atom alloy catalysts and near-frontier molecular orbitals. Journal of the American Chemical Society, 2021, 143(31): 11897–11902

64 Darby M T , Réocreux R , Sykes E C H , Michaelides A , Stamatakis M . Elucidating the stability and reactivity of surface intermediates on single-atom alloy catalysts. ACS Catalysis, 2018, 8(6): 5038–5050

65 Yu S , Cheng X , Wang Y , Xiao B , Xing Y , Ren J , Lu Y , Li H , Zhuang C , Chen G . High activity and selectivity of single palladium atom for oxygen hydrogenation to H₂O₂. Nature Communications, 2022, 13(1): 4737

66 Li W , Wu G , Hu W , Dang J , Wang C , Weng X , da Silva I , Manuel P , Yang S , Guan N . . Direct propylene epoxidation with molecular oxygen over cobalt-containing zeolites. Journal of the American Chemical Society, 2022, 144(9): 4260–4268

67 Qiao B , Liu J , Wang Y G , Lin Q , Liu X , Wang A , Li J , Zhang T , Liu J . Highly efficient catalysis of preferential oxidation of CO in H₂-rich stream by gold single-atom catalysts. ACS Catalysis, 2015, 5(11): 6249–6254

68 Ma W , Mao J , He C T , Shao L , Liu J , Wang M , Yu P , Mao L . Highly selective generation of singlet oxygen from dioxygen with atomically dispersed catalysts. Chemical Science (Cambridge), 2022, 13(19): 5606–5615

69 Shang Q , Tang N , Qi H , Chen S , Xu G , Wu C , Pan X , Wang X , Cong Y . Cong Y. A palladium single-atom catalyst toward efficient activation of molecular oxygen for cinnamyl alcohol oxidation. Chinese Journal of Catalysis, 2020, 41(12): 1812–1817

70 Li Z , Chen Y , Ji S , Tang Y , Chen W , Li A , Zhao J , Xiong Y , Wu Y , Gong Y . . Iridium single-atom catalyst on nitrogen-doped carbon for formic acid oxidation synthesized using a general host-guest strategy. Nature Chemistry, 2020, 12(8): 764–772

71 Xiong Y , Dong J , Huang Z Q , Xin P , Chen W , Wang Y , Li Z , Jin Z , Xing W , Zhuang Z . . Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation. Nature Nanotechnology, 2020, 15(5): 390–397

72 Li W , Madan S E , Réocreux R , Stamatakis M . Elucidating the reactivity of oxygenates on single-atom alloy catalysts. ACS Catalysis, 2023, 13(24): 15851–15868

73 Ni W , Meibom J L , Hassan N U , Chang M , Chu Y C , Krammer A , Sun S , Zheng Y , Bai L , Ma W . . Synergistic interactions between PtRu catalyst and nitrogen-doped carbon support boost hydrogen oxidation. Nature Catalysis, 2023, 6(9): 773–783

74 Meng G , Lan W , Zhang L , Wang S , Zhang T , Zhang S , Xu M , Wang Y , Zhang J , Yue F . . Synergy of single atoms and lewis acid sites for efficient and selective lignin disassembly into monolignol derivatives. Journal of the American Chemical Society, 2023, 145(23): 12884–12893

75 Dong C , Gao Z , Li Y , Peng M , Wang M , Xu Y , Li C , Xu M , Deng Y , Qin X . . Fully exposed palladium cluster catalysts enable hydrogen production from nitrogen heterocycles. Nature Catalysis, 2022, 5(6): 485–493

76 Fu N , Liang X , Wang X , Gan T , Ye C , Li Z , Liu J C , Li Y . Controllable conversion of platinum nanoparticles to single atoms in Pt/CeO₂ by laser ablation for efficient CO oxidation. Journal of the American Chemical Society, 2023, 145(17): 9540–9547

77 Fang Y , Zhang Q , Zhang H , Li X , Chen W , Xu J , Shen H , Yang J , Pan C , Zhu Y . . Dual activation of molecular oxygen and surface lattice oxygen in single atom Cu₁/TiO₂ catalyst for CO oxidation. Angewandte Chemie International Edition, 2022, 61(48): e202212273

78 Niu H , Zhang Z , Wang X , Wan X , Shao C , Guo Y . Theoretical insights into the mechanism of selective nitrate-to-ammonia electroreduction on single-atom catalysts. Advanced Functional Materials, 2021, 31(11): 2008533

79 Leverett J , Tran Phu T , Yuwono J A , Kumar P , Kim C , Zhai Q , Han C , Qu J , Cairney J , Simonov A N . . Tuning the coordination structure of Cu-N-C single atom catalysts for simultaneous electrochemical reduction of CO₂ and NO₃^– to urea. Advanced Energy Materials, 2022, 12(32): 2201500

80 Yang W , Polo Garzon F , Zhou H , Huang Z , Chi M , Meyer H III , Yu X , Li Y , Wu Z . Boosting the activity of Pd single atoms by tuning their local environment on ceria for methane combustion. Angewandte Chemie International Edition, 2023, 62(5): e202217323

81 Jia G , Sun M , Wang Y , Shi Y , Zhang L , Cui X , Huang B , Yu J C . Asymmetric coupled dual-atom sites for selective photoreduction of carbon dioxide to acetic acid. Advanced Functional Materials, 2022, 32(41): 2206817

82 Chu C , Huang D , Gupta S , Weon S , Niu J , Stavitski E , Muhich C , Kim J H . Neighboring Pd single atoms surpass isolated single atoms for selective hydrodehalogenation catalysis. Nature Communications, 2021, 12(1): 5179

83 Liu P , Huang X , Mance D , Copéret C . Atomically dispersed iridium on MgO(111) nanosheets catalyses benzene-ethylene coupling towards styrene. Nature Catalysis, 2021, 4(11): 968–975

84 Ro I , Qi J , Lee S , Xu M , Yan X , Xie Z , Zakem G , Morales A , Chen J G , Pan X . . Bifunctional hydroformylation on heterogeneous Rh-WO_x pair site catalysts. Nature, 2022, 609(7926): 287–292

85 Liu W , Feng H , Yang Y , Niu Y , Wang L , Yin P , Hong S , Zhang B , Zhang X , Wei M . Highly-efficient RuNi single-atom alloy catalysts toward chemoselective hydrogenation of nitroarenes. Nature Communications, 2022, 13(1): 3188

86 Cao H , Zhang Z , Chen J W , Wang Y G . Potential-dependent free energy relationship in interpreting the electrochemical performance of CO₂ reduction on single atom catalysts. ACS Catalysis, 2022, 12(11): 6606–6617

87 Li J , Zeng H , Dong X , Ding Y , Hu S , Zhang R , Dai Y , Cui P , Xiao Z , Zhao D . . Selective CO₂ electrolysis to CO using isolated antimony alloyed copper. Nature Communications, 2023, 14(1): 340

88 Zhang M , Zhang Z , Zhao Z , Huang H , Anjum D H , Wang D , He J , Huang K W . He J h, Huang K W. Tunable selectivity for electrochemical CO₂ reduction by bimetallic Cu-Sn catalysts: elucidating the roles of Cu and Sn. ACS Catalysis, 2021, 11(17): 11103–11108

89 Yang H B , Hung S F , Liu S , Yuan K , Miao S , Zhang L , Huang X , Wang H Y , Cai W , Chen R . . Atomically dispersed Ni(I) as the active site for electrochemical CO₂ reduction. Nature Energy, 2018, 3(2): 140–147

90 Deng Y , Zhao J , Wang S , Chen R , Ding J , Tsai H J , Zeng W J , Hung S F , Xu W , Wang J . . Operando spectroscopic analysis of axial oxygen-coordinated single-Sn-atom sites for electrochemical CO₂ reduction. Journal of the American Chemical Society, 2023, 145(13): 7242–7251

91 Ding J , Bin Yang H , Ma X L , Liu S , Liu W , Mao Q , Huang Y , Li J , Zhang T , Liu B . A tin-based tandem electrocatalyst for CO₂ reduction to ethanol with 80% selectivity. Nature Energy, 2023, 8(12): 1386–1394

92 Zheng X , De Luna P , García de Arquer F P , Zhang B , Becknell N , Ross M B , Li Y , Banis M N , Li Y , Liu M . . Sulfur-modulated tin sites enable highly selective electrochemical reduction of CO₂ to formate. Joule, 2017, 1(4): 794–805

93 Li W , Li L , Xia Q , Hong S , Wang L , Yao Z , Wu T S , Soo Y L , Zhang H , Lo T W B . . Lowering C–C coupling barriers for efficient electrochemical CO₂ reduction to C₂H₄ by jointly engineering single Bi atoms and oxygen vacancies on CuO. Applied Catalysis B: Environmental, 2022, 318: 121823

94 Cao Y , Chen S , Bo S , Fan W , Li J , Jia C , Zhou Z , Liu Q , Zheng L , Zhang F . Single atom Bi decorated copper alloy enables C–C coupling for electrocatalytic reduction of CO₂ into C₂₊ products**. Angewandte Chemie International Edition, 2023, 62(30): e202303048

95 Jiang M , Zhu M , Wang M , He Y , Luo X , Wu C , Zhang L , Jin Z . Review on electrocatalytic coreduction of carbon dioxide and nitrogenous species for urea synthesis. ACS Nano, 2023, 17(4): 3209–3224

96 Zhang X , Zhu X , Bo S , Chen C , Qiu M , Wei X , He N , Xie C , Chen W , Zheng J . . Identifying and tailoring C–N coupling site for efficient urea synthesis over diatomic Fe-Ni catalyst. Nature Communications, 2022, 13(1): 5337

97 LiuYTuXWeiXWangDZhangXChenWChenCWangS. C-bound or O-bound surface: which one boosts electrocatalytic urea synthesis? Angewandte Chemie International Edition, 2023, 62(19): e202300387

98 Li J , Zhang Y , Kuruvinashetti K , Kornienko N . Construction of C–N bonds from small-molecule precursors through heterogeneous electrocatalysis. Nature Reviews. Chemistry, 2022, 6(5): 303–319

99 Liu J , Smith S C , Gu Y , Kou L . C–N coupling enabled by N–N bond breaking for electrochemical urea production. Advanced Functional Materials, 2023, 33(47): 2305894

100 Zhang X , Zhu X , Bo S , Chen C , Cheng K , Zheng J , Li S , Tu X , Chen W , Xie C . . Electrocatalytic urea synthesis with 63.5% faradaic efficiency and 100% N-selectivity via one-step C–N coupling. Angewandte Chemie International Edition, 2023, 62(33): e202305447

101 Chen L , Allec S I , Nguyen M T , Kovarik L , Hoffman A S , Hong J , Meira D , Shi H , Bare S R , Glezakou V A . . Dynamic evolution of palladium single atoms on anatase titania support determines the reverse water-gas shift activity. Journal of the American Chemical Society, 2023, 145(19): 10847–10860

102 Millet M M , Algara Siller G , Wrabetz S , Mazheika A , Girgsdies F , Teschner D , Seitz F , Tarasov A , Levchenko S V , Schlögl R . . Ni single atom catalysts for CO₂ activation. Journal of the American Chemical Society, 2019, 141(6): 2451–2461

103 Du P , Qi R , Zhang Y , Gu Q , Xu X , Tan Y , Liu X , Wang A , Zhu B , Yang B . . Single-atom-driven dynamic carburization over Pd₁-FeO_x catalyst boosting CO₂ conversion. Chem, 2022, 8(12): 3252–3262

104 Yang B , Wang Y , Gao B , Zhang L , Guo L . Size-dependent active site and its catalytic mechanism for CO₂ hydrogenation reactivity and selectivity over Re/TiO₂. ACS Catalysis, 2023, 13(15): 10364–10374

105 Wang D , Yuan Z , Wu X , Xiong W , Ding J , Zhang Z , Huang W . Ni single atoms confined in nitrogen-doped carbon nanotubes for active and selective hydrogenation of CO₂ to CO. ACS Catalysis, 2023, 13(10): 7132–7138

106 Shao X , Yang X , Xu J , Liu S , Miao S , Liu X , Su X , Duan H , Huang Y , Zhang T . Iridium single-atom catalyst performing a quasi-homogeneous hydrogenation transformation of CO₂ to formate. Chem, 2019, 5(3): 693–705

107 Yang T , Mao X , Zhang Y , Wu X , Wang L , Chu M , Pao C W , Yang S , Xu Y , Huang X . Coordination tailoring of Cu single sites on C₃N₄ realizes selective CO₂ hydrogenation at low temperature. Nature Communications, 2021, 12(1): 6022

108 Chen Y , Li H , Zhao W , Zhang W , Li J , Li W , Zheng X , Yan W , Zhang W , Zhu J . . Optimizing reaction paths for methanol synthesis from CO₂ hydrogenation via metal-ligand cooperativity. Nature Communications, 2019, 10(1): 1885

109 Ye X , Yang C , Pan X , Ma J , Zhang Y , Ren Y , Liu X , Li L , Huang Y . Highly selective hydrogenation of CO₂ to ethanol via designed bifunctional Ir₁-In₂O₃ single-atom catalyst. Journal of the American Chemical Society, 2020, 142(45): 19001–19005

110 Zheng K , Li Y , Liu B , Jiang F , Xu Y , Liu X . Ti-doped CeO₂ stabilized single-atom rhodium catalyst for selective and stable CO₂ hydrogenation to ethanol. Angewandte Chemie International Edition, 2022, 61(44): e202210991

111 Gani T Z H , Kulik H J . Understanding and breaking scaling relations in single-site catalysis: methane to methanol conversion by Fe(IV)=O. ACS Catalysis, 2018, 8(2): 975–986

112 Schwach P , Pan X , Bao X . Direct conversion of methane to value-added chemicals over heterogeneous catalysts: challenges and prospects. Chemical Reviews, 2017, 117(13): 8497–8520

113 Tang X , Wang L , Yang B , Fei C , Yao T , Liu W , Lou Y , Dai Q , Cai Y , Cao X M . . Direct oxidation of methane to oxygenates on supported single Cu atom catalyst. Applied Catalysis B: Environmental, 2021, 285: 119827

114 Yang J , Huang Y , Qi H , Zeng C , Jiang Q , Cui Y , Su Y , Du X , Pan X , Liu X . . Modulating the strong metal-support interactian of single-atom catalysts via vicinal structure decoration. Nature Communications, 2022, 13(1): 4244

115 Fang G , Wei F , Lin J , Zhou Y , Sun L , Shang X , Lin S , Wang X . Retrofitting Zr-Oxo nodes of UiO-66 by Ru single atoms to boost methane hydroxylation with nearly total selectivity. Journal of the American Chemical Society, 2023, 145(24): 13169–13180

116 Grundner S , Markovits M A C , Li G , Tromp M , Pidko E A , Hensen E J M , Jentys A , Sanchez Sanchez M , Lercher J A . Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol. Nature Communications, 2015, 6(1): 7546

117 Yu B , Cheng L , Dai S , Jiang Y , Yang B , Li H , Zhao Y , Xu J , Zhang Y , Pan C . . Silver and copper dual single atoms boosting direct oxidation of methane to methanol via synergistic catalysis. Advanced Science, 2023, 10(26): 2302143

118 Shen X , Wu D , Fu X Z , Luo J L . Highly selective conversion of methane to ethanol over CuFe₂O₄-carbon nanotube catalysts at low temperature. Chinese Chemical Letters, 2022, 33(1): 390–393

119 Wang Z , Liu Y , Zhang H , Zhou X . Cubic platinum nanoparticles capped with Cs₂[closo-B₁₂H₁₂] as an effective oxidation catalyst for converting methane to ethanol. Journal of Colloid and Interface Science, 2020, 566: 135–142

120 Zhou Y , Zhang L , Wang W . Direct functionalization of methane into ethanol over copper modified polymeric carbon nitride via photocatalysis. Nature Communications, 2019, 10(1): 506

121 Su J , Musgrave C B III , Song Y , Huang L , Liu Y , Li G , Xin Y , Xiong P , Li M M J , Wu H . . Strain enhances the activity of molecular electrocatalysts via carbon nanotube supports. Nature Catalysis, 2023, 6(9): 818–828

122 Zhou S , Ma W , Anjum U , Kosari M , Xi S , Kozlov S M , Zeng H C . Strained few-layer MoS₂ with atomic copper and selectively exposed in-plane sulfur vacancies for CO₂ hydrogenation to methanol. Nature Communications, 2023, 14(1): 5872

123 Shamzhy M , Opanasenko M , Concepción P , Martínez A . New trends in tailoring active sites in zeolite-based catalysts. Chemical Society Reviews, 2019, 48(4): 1095–1149

124 Deng X , Qin B , Liu R , Qin X , Dai W , Wu G , Guan N , Ma D , Li L . Zeolite-eencaged isolated platinum ions enable heterolytic dihydrogen activation and selective hydrogenations. Journal of the American Chemical Society, 2021, 143(49): 20898–20906

125 Han B , Guo Y , Huang Y , Xi W , Xu J , Luo J , Qi H , Ren Y , Liu X , Qiao B . . Strong metal-support interactions between Pt single atoms and TiO₂. Angewandte Chemie International Edition, 2020, 59(29): 11824–11829

126 Yang J , Li W , Wang D , Li Y . Electronic metal-support interaction of single-atom catalysts and applications in electrocatalysis. Advanced Materials, 2020, 32(49): 2003300

127 Wakerley D , Lamaison S , Ozanam F , Menguy N , Mercier D , Marcus P , Fontecave M , Mougel V . Bio-inspired hydrophobicity promotes CO₂ reduction on a Cu surface. Nature Materials, 2019, 18(11): 1222–1227

128 Li X , Cao C S , Hung S F , Lu Y R , Cai W , Rykov A I , Miao S , Xi S , Yang H , Hu Z . . Identification of the electronic and structural dynamics of catalytic centers in single-Fe-atom material. Chem, 2020, 6(12): 3440–3454

129 Ren X , Zhao J , Li X , Shao J , Pan B , Salamé A , Boutin E , Groizard T , Wang S , Ding J . . In-situ spectroscopic probe of the intrinsic structure feature of single-atom center in electrochemical CO/CO₂ reduction to methanol. Nature Communications, 2023, 14(1): 3401