Defect engineering on constructing surface active sites in catalysts for environment and energy applications

Abstract

The precise engineering of surface active sites is deemed as an efficient protocol for regulating surfaces and catalytic properties of catalysts. Defect engineering is the most feasible option to modulate the surface active sites of catalysts. Creating specific active sites on the catalyst allows precise modulation of its electronic structure and physicochemical characteristics. Here, we outlined the engineering of several types of defects, including vacancy defects, void defects, dopant-related defects, and defect-based single atomic sites. An overview of progress in fabricating structural defects on catalysts via de novo synthesis or post-synthetic modification was provided. Then, the applications of the well-designed defective catalysts in energy conversion and environmental remediation were carefully elucidated. Finally, current challenges in the precise construction of active defect sites on the catalyst and future perspectives for the development directions of precisely controlled synthesis of defective catalysts were also proposed.

Key words： defect engineering; vacancy; void defects; doping; single atomic sites

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

We gratefully acknowledge funding support from the National Science Foundation of China (Grant No. 22306124), the Beijing Outstanding Young Scientist Program.

References

1 Beller M , Centi G . Catalysis and sustainable development: the marriage for innovation. ChemSusChem, 2009, 2(6): 459–460

2 Linares N , Silvestre-Albero A M , Serrano E , Silvestre-Albero J , García-Martínez J . Mesoporous materials for clean energy technologies. Chemical Society Reviews, 2014, 43(22): 7681–7717

3 Roduner E . Understanding catalysis. Chemical Society Reviews, 2014, 43(24): 8226–8239

4 Vogt C , Weckhuysen B M . The concept of active site in heterogeneous catalysis. Nature Reviews Chemistry, 2022, 6(2): 89–111

5 Wang Y , Chen L , Cao H , Chi Z , Chen C , Duan X , Xie Y , Qi F , Song W , Liu J . . Role of oxygen vacancies and Mn sites in hierarchical Mn₂O₃/LaMnO_3–δ perovskite composites for aqueous organic pollutants decontamination. Applied Catalysis B: Environmental, 2019, 245: 546–554

6 Hattori H . Solid base catalysts: generation of basic sites and application to organic synthesis. Applied Catalysis A, General, 2001, 222(1-2): 247–259

7 Wachs I E , Roberts C A . Monitoring surface metal oxide catalytic active sites with Raman spectroscopy. Chemical Society Reviews, 2010, 39(12): 5002–5017

8 Du Y , Sheng H , Astruc D , Zhu M . Atomically precise noble metal nanoclusters as efficient catalysts: a bridge between structure and properties. Chemical Reviews, 2020, 120(2): 526–622

9 Kröger F . Defect chemistry in crystalline solids. Annual Review of Materials Science, 1977, 7(1): 449–475

10 Tang T , Wang Z , Guan J . A review of defect engineering in two-dimensional materials for electrocatalytic hydrogen evolution reaction. Chinese Journal of Catalysis, 2022, 43(3): 636–678

11 Thomas J M , Raja R , Lewis D W . Single-site heterogeneous catalysts. Angewandte Chemie International Edition, 2005, 44(40): 6456–6482

12 Liu L , Corma A . Structural transformations of solid electrocatalysts and photocatalysts. Nature Reviews Chemistry, 2021, 5(4): 256–276

13 Zambelli T , Wintterlin J , Trost J , Ertl G . Identification of the “active sites” of a surface-catalyzed reaction. Science, 1996, 273(5282): 1688–1690

14 Sun Y , Gao S , Lei F , Xie Y . Atomically-thin two-dimensional sheets for understanding active sites in catalysis. Chemical Society Reviews, 2015, 44(3): 623–636

15 Yan D , Li Y , Huo J , Chen R , Dai L , Wang S . Defect chemistry of nonprecious-metal electrocatalysts for oxygen reactions. Advanced Materials, 2017, 29(48): 1606459

16 Xie C , Yan D , Li H , Du S , Chen W , Wang Y , Zou Y , Chen R , Wang S . Defect chemistry in heterogeneous catalysis: recognition, understanding, and utilization. ACS Catalysis, 2020, 10(19): 11082–11098

17 Lannoo M , Bourgoin J . Atomic configuration of point defects. In: Point Defects in Semiconductors I. Springer Series in Solid-State Sciences. Berlin, Heidelberg: Springer-Verlag, 1981, 22: 1–35

18 Leonardi A , Scardi P . Dislocation effects on the diffraction line profiles from nanocrystalline domains. Metallurgical and Materials Transactions. A, Physical Metallurgy and Materials Science, 2016, 47(12): 5722–5732

19 Hemesath E R , Schreiber D K , Gulsoy E B , Kisielowski C F , Petford-Long A K , Voorhees P W , Lauhon L J . Catalyst incorporation at defects during nanowire growth. Nano Letters, 2012, 12(1): 167–171

20 Rudolph P . Fundamentals and engineering of defects. Progress in Crystal Growth and Characterization of Materials, 2016, 62(2): 89–110

21 Murakami Y . Material defects as the basis of fatigue design. International Journal of Fatigue, 2012, 41: 2–10

22 Schlögl R . Heterogeneous catalysis. Angewandte Chemie International Edition, 2015, 54(11): 3465–3520

23 Zhang Y , Gao F , You H , Li Z , Zou B , Du Y . Recent advances in one-dimensional noble-metal-based catalysts with multiple structures for efficient fuel-cell electrocatalysis. Coordination Chemistry Reviews, 2022, 450: 214244

24 Wang B , Liu J , Yao S , Liu F , Li Y , He J , Lin Z , Huang F , Liu C , Wang M . Vacancy engineering in nanostructured semiconductors for enhancing photocatalysis. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2021, 9(32): 17143–17172

25 Sun Y , Wang H , Xing Q , Cui W , Li J , Wu S , Sun L . The pivotal effects of oxygen vacancy on Bi₂MoO₆: promoted visible light photocatalytic activity and reaction mechanism. Chinese Journal of Catalysis, 2019, 40(5): 647–655

26 Guan S , Wang L , Xu S , Yang D , Waterhouse G I N , Qu X , Zhou S . Vacancy-enhanced generation of singlet oxygen for photodynamic therapy. Chemical Science, 2019, 10(8): 2336–2341

27 Zheng X , Li Y , Zhang L , Shen L , Xiao Y , Zhang Y , Au C , Jiang L . Insight into the effect of morphology on catalytic performance of porous CeO₂ nanocrystals for H₂S selective oxidation. Applied Catalysis B: Environmental, 2019, 252: 98–110

28 Zhou S , Jin W , Ding Y , Shao B , Wang B , Hu X , Kong Y . In-situ intercalation of Au nanoparticles and magnetic γ-Fe₂O₃ in the walls of MCM-41 with abundant void defects for highly efficient reduction of 4-nitrophenol and organic dyes. Dalton Transactions, 2018, 47(47): 16862–16875

29 Tang Q , Ma Y , Wang J . The active sites engineering of catalysts for CO₂ activation and conversion. Solar RRL, 2021, 5(2): 2000443

30 Connell G , Dumesic J A . The generation of Brønsted and Lewis acid sites on the surface of silica by addition of dopant cations. Journal of Catalysis, 1987, 105(2): 285–298

31 Lee J , Kumar A , Kim M G , Yang T , Shao X , Liu X , Liu Y , Hong Y , Jadhav A R , Liang M . . Single-metal-atom dopants increase the Lewis acidity of metal oxides and promote nitrogen fixation. ACS Energy Letters, 2021, 6(12): 4299–4308

32 Zhang Y , Guo L , Tao L , Lu Y , Wang S . Defect-based single-atom electrocatalysts. Small Methods, 2019, 3(9): 1800406

33 Xue Q , Xie Y , Wu S , Wu T , Soo Y , Day S , Tang C C , Man H W , Yuen S T , Wong K . . A rational study on the geometric and electronic properties of single-atom catalysts for enhanced catalytic performance. Nanoscale, 2020, 12(45): 23206–23212

34 Xi J , Jung H S , Xu Y , Xiao F , Bae J W , Wang S . Synthesis strategies, catalytic applications, and performance regulation of single-atom catalysts. Advanced Functional Materials, 2021, 31(12): 2008318

35 Liu D , He Q , Ding S , Song L . Structural regulation and support coupling effect of single-atom catalysts for heterogeneous catalysis. Advanced Energy Materials, 2020, 10(32): 2001482

36 Lang R , Du X , Huang Y , Jiang X , Zhang Q , Guo Y , Liu K , Qiao B , Wang A , Zhang T . Single-atom catalysts based on the metal-oxide interaction. Chemical Reviews, 2020, 120(21): 11986–12043

37 Bai S , Zhang N , Gao C , Xiong Y . Defect engineering in photocatalytic materials. Nano Energy, 2018, 53: 296–336

38 Zhuang G , Yan J , Wen Y , Zhuang Z , Yu Y . Two-dimensional transition metal oxides and chalcogenides for advanced photocatalysis: progress, challenges, and opportunities. Solar RRL, 2021, 5(6): 2000403

39 Zhou Y , Wang F , Zhou J , Dong B , Dong Y , Liu X , Liu B , Yu J , Chai Y . Triple captured iron by defect abundant NiO for efficient water oxidation. Inorganic Chemistry Frontiers, 2022, 9(6): 1281–1292

40 Gao W , Chi J , Wang Z , Lin J , Liu D , Zeng J , Yu J , Wang L , Chai Y , Dong B . Optimized bimetallic nickel-iron phosphides with rich defects as enhanced electrocatalysts for oxygen evolution reaction. Journal of Colloid and Interface Science, 2019, 537: 11–19

41 Ye G , Wan L , Zhang Q , Liu H , Zhou J , Wu L , Zeng X , Wang H , Chen X , Wang J . Boosting catalytic performance of MOF-808(Zr) by direct generation of rich defective Zr nodes via a solvent-free approach. Inorganic Chemistry, 2023, 62(10): 4248–4259

42 Fang Z , Bueken B , De Vos D E , Fischer R A . Defect-engineered metal-organic frameworks. Angewandte Chemie International Edition, 2015, 54(25): 7234–7254

43 ShollD SLivelyR P. Defects in metal-organic frameworks: challenge or opportunity? Journal of Physical Chemistry Letters, 2015, 6(17): 3437–3444

44 Gao P , Chen Z , Gong Y , Zhang R , Liu H , Tang P , Chen X , Passerini S , Liu J . The role of cation vacancies in electrode materials for enhanced electrochemical energy storage: synthesis, advanced characterization, and fundamentals. Advanced Energy Materials, 2020, 10(14): 1903780

45 Pang Q , Yang L , Li Q . Vacancies in metal-organic frameworks: formation, arrangement, and functions. Small Structures, 2022, 3(5): 2100203

46 Wu Y , Li Y , Gao J , Zhang Q . Recent advances in vacancy engineering of metal-organic frameworks and their derivatives for electrocatalysis. SusMat, 2021, 1(1): 66–87

47 Ren J , Ledwaba M , Musyoka N M , Langmi H W , Mathe M , Liao S , Pang W . Structural defects in metal-organic frameworks (MOFs): formation, detection and control towards practices of interests. Coordination Chemistry Reviews, 2017, 349: 169–197

48 Cirujano F G , Martin N , Wee L H . Design of hierarchical architectures in metal-oganic frameworks for catalysis and adsorption. Chemistry of Materials, 2020, 32(24): 10268–10295

49 Lázaro I A , Szalad H , Valiente P , Albero J , García H , Martí-Gastaldo C . Tuning the photocatalytic activity of Ti-based metal-organic frameworks through modulator defect-engineered functionalization. ACS Applied Materials & Interfaces, 2022, 14(18): 21007–21017

50 Wei R , Gaggioli C A , Li G , Islamoglu T , Zhang Z , Yu P , Farha O K , Cramer C J , Gagliardi L , Yang D . . Tuning the properties of Zr₆O₈ nodes in the metal organic framework UiO-66 by selection of node-bound ligands and linkers. Chemistry of Materials, 2019, 31(5): 1655–1663

51 Barin G , Krungleviciute V , Gutov O , Hupp J T , Yildirim T , Farha O K . Defect creation by linker fragmentation in metal-organic frameworks and its effects on gas uptake properties. Inorganic Chemistry, 2014, 53(13): 6914–6919

52 El-Gamel N E . Generation of defect-modulated metal-organic frameworks by fragmented-linker co-assembly of CPO-27(M) frameworks. European Journal of Inorganic Chemistry, 2015, 2015(8): 1351–1358

53 Fan Z , Wang J , Wang W , Burger S , Wang Z , Wang Y , Wöll C , Cokoja M , Fischer R A . Defect engineering of copper paddlewheel-based metal-organic frameworks of type NOTT-100: implementing truncated linkers and its effect on catalytic properties. ACS Applied Materials & Interfaces, 2020, 12(34): 37993–38002

54 Lei L , Huang D , Cheng M , Deng R , Chen S , Chen Y , Wang W . Defects engineering of bimetallic Ni-based catalysts for electrochemical energy conversion. Coordination Chemistry Reviews, 2020, 418: 213372

55 Zhang X , Zhang Z , Huang H , Wang Y , Tong N , Lin J , Liu D , Wang X . Oxygen vacancy modulation of two-dimensional γ-Ga₂O₃ nanosheets as efficient catalysts for photocatalytic hydrogen evolution. Nanoscale, 2018, 10(45): 21509–21517

56 Chen S , Huang H , Zhao D , Zhou J , Yu J , Qu B , Liu Q , Sun H , Zhao J . Direct growth of polycrystalline GaN porous layer with rich nitrogen vacancies: application to catalyst-free electrochemical detection. ACS Applied Materials & Interfaces, 2020, 12(48): 53807–53815

57 Wang J , Lin S , Tian N , Ma T , Zhang Y , Huang H . Nanostructured metal sulfides: classification, modification strategy, and solar-driven CO₂ reduction application. Advanced Functional Materials, 2021, 31(9): 2008008

58 Jing X , Lu N , Huang J , Zhang P , Zhang Z . One-step hydrothermal synthesis of S-defect-controlled ZnIn₂S₄ microflowers with improved kinetics process of charge-carriers for photocatalytic H₂ evolution. Journal of Energy Chemistry, 2021, 58: 397–407

59 Li K , Yang J , Gu J . Hierarchically porous MOFs synthesized by soft-template strategies. Accounts of Chemical Research, 2022, 55(16): 2235–2247

60 Cai G , Jiang H L . A modulator-induced defect-formation strategy to hierarchically porous metal-organic frameworks with high stability. Angewandte Chemie International Edition, 2017, 56(2): 563–567

61 Yuan D , Zhao D , Sun D , Zhou H . An isoreticular series of metal-organic frameworks with dendritic hexacarboxylate ligands and exceptionally high gas-uptake capacity. Angewandte Chemie, 2010, 122(31): 5485–5489

62 Zhao D , Yuan D , Sun D , Zhou H . Stabilization of metal-organic frameworks with high surface areas by the incorporation of mesocavities with microwindows. Journal of the American Chemical Society, 2009, 131(26): 9186–9188

63 Farha O K , Yazaydın A Ö , Eryazici I , Malliakas C D , Hauser B G , Kanatzidis M G , Nguyen S T , Snurr R Q , Hupp J T . De novo synthesis of a metal-organic framework material featuring ultrahigh surface area and gas storage capacities. Nature Chemistry, 2010, 2(11): 944–948

64 Furukawa H , Ko N , Go Y B , Aratani N , Choi S B , Choi E , Yazaydin A Ö , Snurr R Q , O’Keeffe M , Kim J . . Ultrahigh porosity in metal-organic frameworks. Science, 2010, 329(5990): 424–428

65 Li M , Liu Y , Li F , Shen C , Kaneti Y V , Yamauchi Y , Yuliarto B , Chen B , Wang C . Defect-rich hierarchical porous UiO-66(Zr) for tunable phosphate removal. Environmental Science & Technology, 2021, 55(19): 13209–13218

66 Tang C , Wang H , Chen X , Li B , Hou T , Zhang B , Zhang Q , Titirici M , Wei F . Topological defects in metal-free nanocarbon for oxygen electrocatalysis. Advanced Materials, 2016, 28(32): 6845–6851

67 Zoller F , Häringer S , Böhm D , Luxa J , Sofer Z , Fattakhova-Rohlfing D . Carbonaceous oxygen evolution reaction catalysts: from defect and doping-induced activity over hybrid compounds to ordered framework structures. Small, 2021, 17(48): 2007484

68 Zhang A , Liang Y , Zhang H , Geng Z , Zeng J . Doping regulation in transition metal compounds for electrocatalysis. Chemical Society Reviews, 2021, 50(17): 9817–9844

69 Karakitsou K E , Verykios X E . Effects of altervalent cation doping of titania on its performance as a photocatalyst for water cleavage. Journal of Physical Chemistry, 1993, 97(6): 1184–1189

70 Shen Z , Jin X , Tian J , Li M , Yuan Y , Zhang S , Fang S , Fan X , Xu W , Lu H . . Cation-doped ZnS catalysts for polysulfide conversion in lithium-sulfur batteries. Nature Catalysis, 2022, 5(6): 555–563

71 Xie J , Lü Q , Qiao W , Bu C , Zhang Y , Zhai X , Lü R , Chai Y , Dong B . Enhancing cobalt-oxygen bond to stabilize defective Co₂MnO₄ in acidic oxygen evolution. Acta Physico-Chimica Sinica, 2024, 40(3): 2305021

72 Sun Y , Xu K , Wei Z , Li H , Zhang T , Li X , Cai W , Ma J , Fan H J , Li Y . Strong electronic interaction in dual-cation-incorporated NiSe₂ nanosheets with lattice distortion for highly efficient overall water splitting. Advanced Materials, 2018, 30(35): 1802121

73 Patnaik S , Sahoo D P , Parida K . Recent advances in anion doped g-C₃N₄ photocatalysts: a review. Carbon, 2021, 172: 682–711

74 Jiang L , Yuan X , Pan Y , Liang J , Zeng G , Wu Z , Wang H . Doping of graphitic carbon nitride for photocatalysis: a reveiw. Applied Catalysis B: Environmental, 2017, 217: 388–406

75 Lu C , Zhang P , Jiang S , Wu X , Song S , Zhu M , Lou Z , Li Z , Liu F , Liu Y . . Photocatalytic reduction elimination of UO₂²⁺ pollutant under visible light with metal-free sulfur doped g-C₃N₄ photocatalyst. Applied Catalysis B: Environmental, 2017, 200: 378–385

76 Xu H , Zhang T , Wang D , Cai D , Chen S , Wang H , Shu S , Zhu Y . Degradation of tetracycline using persulfate activated by a honeycomb structured S-doped g-C₃N₄/biochar under visible light. Separation and Purification Technology, 2022, 300: 121833

77 Hasija V , Singh P , Thakur S , Stando K , Nguyen V , Van Le Q , Alshehri S M , Ahamad T , Wu K C , Raizada P . Oxygen doping facilitated N-vacancies in g-C₃N₄ regulates electronic band gap structure for trimethoprim and Cr(VI) mitigation: simulation studies and photocatalytic degradation pathways. Applied Materials Today, 2022, 29: 101676

78 Zhang X , Li F , Fan R , Zhao J , Dong B , Wang F , Liu H , Yu J , Liu C , Chai Y F . P double-doped Fe₃O₄ with abundant defect sites for efficient hydrogen evolution at high current density. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2021, 9(28): 15836–15845

79 Rong H , Zhan T , Sun Y , Wen Y , Liu X , Teng H . ZIF-8 derived nitrogen, phosphorus and sulfur tri-doped mesoporous carbon for boosting electrocatalysis to oxygen reduction in universal pH range. Electrochimica Acta, 2019, 318: 783–793

80 Tian L , Pang X , Xu H , Liu D , Lu X , Li J , Wang J , Li Z . Cation-anion dual doping modifying electronic structure of hollow CoP nanoboxes for enhanced water oxidation electrocatalysis. Inorganic Chemistry, 2022, 61(42): 16944–16951

81 Yuan C , Xu T , Guo M , Zhang T , Yu X . Cation/anion-doping induced electronic structure regulation strategy to boost the catalytic hydrogen evolution from ammonia borane hydrolysis. Applied Catalysis B: Environmental, 2023, 321: 122044

82 Wang P , Ma X , Hao X , Tang B , Abudula A , Guan G . Oxygen vacancy defect engineering to promote catalytic activity toward the oxidation of VOCs: a critical review. Catalysis Reviews, 2022, 66(2): 586–639

83 Huang Y , Yu Y , Yu Y , Zhang B . Oxygen vacancy engineering in photocatalysis. Solar RRL, 2020, 4(8): 2000037

84 Fu L , Chen H , Wang K , Wang X . Oxygen-vacancy generation in MgFe₂O₄ by high temperature calcination and its improved photocatalytic activity for CO₂ reduction. Journal of Alloys and Compounds, 2022, 891: 161925

85 Su L , Zhang Y , Zhan X , Zhang L , Zhao Y , Zhu X , Wu H , Chen H , Shen C , Wang L . Pr₆O₁₁: temperature-dependent oxygen vacancy regulation and catalytic performance for lithium-oxygen batteries. ACS Applied Materials & Interfaces, 2022, 14(36): 40975–40984

86 Li Z , Yan Q , Jiang Q , Gao Y , Xue T , Li R , Liu Y , Wang Q . Oxygen vacancy mediated Cu_yCo_3–yFe₁O_x mixed oxide as highly active and stable toluene oxidation catalyst by multiple phase interfaces formation and metal doping effect. Applied Catalysis B: Environmental, 2020, 269: 118827

87 Xie Q , Wang M , Xu Y , Li X , Zhou X , Hong L , Jiang L , Lin W . S vacancy modulated Zn_xCd_1–xS/CoP quantum dots for efficient H₂ evolution from water splitting under visible light. Journal of Energy Chemistry, 2021, 61: 210–218

88 Zhang R , Ning X , Wang Z , Zhao H , He Y , Han Z , Du P , Lu X . Significantly promoting the photogenerated charge separation by introducing an oxygen vacancy regulation strategy on the FeNiOOH co-catalyst. Small, 2022, 18(20): 2107938

89 Chang Y , Huang H , Yang T , Wang L , Zhu H , Zhong C . Simultaneous introduction of oxygen vacancies and hierarchical pores into titanium-based metal-organic framework for enhanced photocatalytic performance. Journal of Colloid and Interface Science, 2021, 599: 785–794

90 Gao W , Li S , He H , Li X , Cheng Z , Yang Y , Wang J , Shen Q , Wang X , Xiong Y . . Vacancy-defect modulated pathway of photoreduction of CO₂ on single atomically thin AgInP₂S₆ sheets into olefiant gas. Nature Communications, 2021, 12(1): 4747

91 Yi L , Chen L , Lu C , Ni Y , Xu Z . Effects of oxygen defects on structure and properties of Sm_0.5Sr_0.5CoO_3–δ annealed in different atmospheres. Journal of Rare Earths, 2013, 31(12): 1183–1190

92 Wang K , Chang Y , Lv L , Long Y . Effect of annealing temperature on oxygen vacancy concentrations of nanocrystalline CeO₂ film. Applied Surface Science, 2015, 351: 164–168

93 Li Q , Zhu X , Yang J , Yu Q , Zhu X , Chu J , Du Y , Wang C , Hua Y , Li H . . Plasma treated Bi₂WO₆ ultrathin nanosheets with oxygen vacancies for improved photocatalytic CO₂ reduction. Inorganic Chemistry Frontiers, 2020, 7(3): 597–602

94 Li X , Zhang J , Zhou F , Zhang H , Bai J , Wang Y , Wang H . Preparation of N-vacancy-doped g-C₃N₄ with outstanding photocatalytic H₂O₂ production ability by dielectric barrier discharge plasma treatment. Chinese Journal of Catalysis, 2018, 39(6): 1090–1098

95 Wu L , Li Y , Fu Z , Su B . Hierarchically structured porous materials: synthesis strategies and applications in energy storage. National Science Review, 2020, 7(11): 1667–1701

96 Huang H , Li J , Wang K , Han T , Tong M , Li L , Xie Y , Yang Q , Liu D , Zhong C . An in situ self-assembly template strategy for the preparation of hierarchical-pore metal-organic frameworks. Nature Communications, 2015, 6(1): 8847

97 Kirchon A , Li J , Xia F , Day G S , Becker B , Chen W , Sue H , Fang Y , Zhou H . Modulation versus templating: fine-tuning of hierarchally porous PCN-250 using fatty acids to engineer guest adsorption. Angewandte Chemie International Edition, 2019, 58(36): 12425–12430

98 Hu M , Ju Y , Liang K , Suma T , Cui J , Caruso F . Void engineering in metal-organic frameworks via synergistic etching and surface functionalization. Advanced Functional Materials, 2016, 26(32): 5827–5834

99 Liang X , Fu N , Yao S , Li Z , Li Y . The progress and outlook of metal single-atom-site catalysis. Journal of the American Chemical Society, 2022, 144(40): 18155–18174

100 Pan Y , Zhang C , Liu Z , Chen C , Li Y . Structural regulation with atomic-level precision: from single-atomic site to diatomic and atomic interface catalysis. Matter, 2020, 2(1): 78–110

101 Rong X , Wang H , Lu X , Si R , Lu T . Controlled synthesis of a vacancy-defect single-atom catalyst for boosting CO₂ electroreduction. Angewandte Chemie, 2020, 132(5): 1977–1981

102 Ji S , Chen Y , Wang X , Zhang Z , Wang D , Li Y . Chemical synthesis of single atomic site catalysts. Chemical Reviews, 2020, 120(21): 11900–11955

103 Yuan L , Tang T , Hu J , Wan L . Confinement strategies for precise synthesis of efficient electrocatalysts from the macroscopic to the atomic level. Accounts of Materials Research, 2021, 2(10): 907–919

104 Chen Y , Ji S , Chen C , Peng Q , Wang D , Li Y . Single-atom catalysts: synthetic strategies and electrochemical applications. Joule, 2018, 2(7): 1242–1264

105 Liang S , Zou L , Zheng L , Li L , Wang X , Song L , Xu J . Highly stable Co single atom confined in hierarchical carbon molecular sieve as efficient electrocatalysts in metal-air batteries. Advanced Energy Materials, 2022, 12(11): 2103097

106 Cheng X , Wang J , Zhao K , Bi Y . Spatially confined iron single-atom and potassium ion in carbon nitride toward efficient CO₂ reduction. Applied Catalysis B: Environmental, 2022, 316: 121643

107 Mo Q , Zhang L , Li S , Song H , Fan Y , Su C . Engineering single-atom sites into pore-confined nanospaces of porphyrinic metal-organic frameworks for the highly efficient photocatalytic hydrogen evolution reaction. Journal of the American Chemical Society, 2022, 144(49): 22747–22758

108 Wang Y , Wang D , Li Y . Rational design of single-atom site electrocatalysts: from theoretical understandings to practical applications. Advanced Materials, 2021, 33(34): 2008151

109 Wan J , Chen W , Jia C , Zheng L , Dong J , Zheng X , Wang Y , Yan W , Chen C , Peng Q . . Defect effects on TiO₂ nanosheets: stabilizing single atomic site Au and promoting catalytic properties. Advanced Materials, 2018, 30(11): 1705369

110 Jin J , Han X , Fang Y , Zhang Z , Li Y , Zhang T , Han A , Liu J . Microenvironment engineering of Ru single-atom catalysts by regulating the cation vacancies in NiFe-layered double hydroxides. Advanced Functional Materials, 2022, 32(8): 2109218

111 Chen Z , Li X , Zhao J , Zhang S , Wang J , Zhang H , Zhang J , Dong Q , Zhang W , Hu W . . Stabilizing Pt single atoms through Pt-Se electron bridges on vacancy-enriched nickel selenide for efficient electrocatalytic hydrogen evolution. Angewandte Chemie International Edition, 2023, 62(39): e202308686

112 Hejazi S , Mehdi-pour H , Otieno C O , Müller J , Pour-Ali S , Shahsanaei M , Tafreshi S S , Butz B , Killian M S , Mohajernia S . Room-temperature defect-engineered titania: an efficient platform for Pt single atom decoration for photocatalytic H₂ evolution. International Journal of Hydrogen Energy, 2024, 51: 222–233

113 Geng L , Zhang Q , Wang X , Han H , Zhang Y , Li C , Li Z , Zhang D , Zhang X , Abdukayum A . . Electronic modulation induced by oxygen vacancy creating in copper oxides toward accelerated hydrogenation kinetics of nitroaromatics. Applied Catalysis B: Environmental, 2024, 343: 123575

114 Huang H , Cho A , Kim S , Jun H , Lee A , Han J W , Lee J . Structural design of amorphous CoMoP_x with abundant active sites and synergistic catalysis effect for effective water splitting. Advanced Functional Materials, 2020, 30(43): 2003889

115 Liu W , Luo C , Zhang S , Zhang B , Ma J , Wang X , Liu W , Li Z , Yang Q , Lv W . Cobalt-doping of molybdenum disulfide for enhanced catalytic polysulfide conversion in lithium-sulfur batteries. ACS Nano, 2021, 15(4): 7491–7499

116 Zhong X , Yi W , Qu Y , Zhang L , Bai H , Zhu Y , Wan J , Chen S , Yang M , Huang L . . Co single-atom anchored on Co₃O₄ and nitrogen-doped active carbon toward bifunctional catalyst for zinc-air batteries. Applied Catalysis B: Environmental, 2020, 260: 118188

117 Yang H , Liu X , Hao M , Xie Y , Wang X , Tian H , Waterhouse G I N , Kruger P E , Telfer S G , Ma S . Functionalized iron-nitrogen-carbon electrocatalyst provides a reversible electron transfer platform for efficient uranium extraction from seawater. Advanced Materials, 2021, 33(51): 2106621

118 Yang H , Liu Y , Liu X , Wang X , Tian H , Waterhouse G I N , Kruger P E , Telfer S G , Ma S . Large-scale synthesis of N-doped carbon capsules supporting atomically dispersed iron for efficient oxygen reduction reaction electrocatalysis. eScience, 2022, 2(2): 227–234

119 Liu X , Xie Y , Hao M , Chen Z , Yang H , Waterhouse G I N , Ma S , Wang X . Highly efficient electrocatalytic uranium extraction from seawater over an amidoxime-functionalized In-N-C catalyst. Advanced Science (Weinheim, Baden-Wurttemberg, Germany), 2022, 9(23): 2201735

120 Liu X , Xie Y , Li Y , Hao M , Chen Z , Yang H , Waterhouse G I N , Ma S , Wang X . Functional carbon capsules supporting ruthenium nanoclusters for efficient electrocatalytic ⁹⁹TcO₄-/ReO₄- removal from acidic and alkaline nuclear wastes. Advanced Science, 2023, 10(30): 2303536

121 Gao W , Yang M , Chi J , Zhang X , Xie J , Guo B , Wang L , Chai Y , Dong B . In situ construction of surface defects of carbon-doped ternary cobalt-nickel-iron phosphide nanocubes for efficient overall water splitting. Science China Materials, 2019, 62: 1285–1296

122 Zhao G , Busser G M , Froese C , Hu B , Bonke S A , Schnegg A , Ai Y , Wei D , Wang X , Peng B . . Anaerobic alcohol conversion to carbonyl compounds over nanoscaled Rh-doped SrTiO₃ under visible light. Journal of Physical Chemistry Letters, 2019, 10(9): 2075–2080

123 Hu Y , Zhao G , Pan Q , Wang H , Shen Z , Peng B , Busser G W , Wang X , Muhler M . Highly selective anaerobic oxidation of alcohols over Fe‐doped SrTiO₃ under visible light. ChemCatChem, 2019, 11(20): 5139–5144

124 Li B , Hong J , Ai Y , Hu Y , Shen Z , Li S , Zou Y , Zhang S , Wang X , Zhao G . . Visible-near-infrared-light-driven selective oxidation of alcohols over nanostructured Cu doped SrTiO₃ in water under mild condition. Journal of Catalysis, 2021, 399: 142–149

125 Shen Z , Hu Y , Pan Q , Huang C , Zhu B , Xia W , Wang H , Yue J , Muhler M , Zhao G . . Oxygen vacancies-enriched Ta-doped Bi₂WO₆ with Pt as cocatalyst for boosting the dehydrogenation of benzyl alcohol in water. Applied Surface Science, 2022, 571: 151370

126 Zou Y , Hu Y , Uhrich A , Shen Z , Peng B , Ji Z , Muhler M , Zhao G , Wang X , Xu X . Steering accessible oxygen vacancies for alcohol oxidation over defective Nb₂O₅ under visible light illumination. Applied Catalysis B: Environmental, 2021, 298: 120584

127 Zhang S , Liu Y , Gu P , Ma R , Wen T , Zhao G , Li L , Ai Y , Hu C , Wang X . Enhanced photodegradation of toxic organic pollutants using dual-oxygen-doped porous g-C₃N₄: mechanism exploration from both experimental and DFT studies. Applied Catalysis B: Environmental, 2019, 248: 1–10

128 Zhang S , Liu Y , Ma R , Jia D , Wen T , Ai Y , Zhao G , Fang F , Hu B , Wang X . Molybdenum(VI)-oxo clusters incorporation activates g-C₃N₄ with simultaneously regulating charge transfer and reaction centers for boosting photocatalytic performance. Advanced Functional Materials, 2022, 32(38): 2204175

129 Li C , Guo Y , Tang D , Guo Y , Wang G , Jiang H , Li J . Optimizing electron structure of Zn-doped AgFeO₂ with abundant oxygen vacancies to boost photocatalytic activity for Cr(VI) reduction and organic pollutants decomposition: DFT insights and experimental. Chemical Engineering Journal, 2021, 411: 128515