Emerging two-dimensional metallenes: Recent advances in structural regulations and electrocatalytic applications

doi:10.1016/S1872-2067(21)64022-6

Abstract

Abstract:

Benefiting from the ultrahigh specific surface areas, highly accessible surface atoms, and highly tunable microscopic structures, the two-dimensional metallenes as nanocatalysts have displayed promising performance for various electrocatalytic reactions. Herein, we reviewed recent advances on metallenes in structural regulations including defect, phase, strain, interface, doping, and alloying engineering strategies and their applications in energy electrocatalytic reactions involving oxygen reduction reaction, carbon dioxide reduction reaction, hydrogen evolution reaction, and small molecules oxidation reaction. Finally, we proposed the future challenges and directions in this emerging area.

Key words: Metallenes, Ultrathin nanosheets, Structurally regulating strategy, Electrocatalysis, Enhancement mechanism

Jiandong Wu, Xiao Zhao, Xiaoqiang Cui, Weitao Zheng. Emerging two-dimensional metallenes: Recent advances in structural regulations and electrocatalytic applications[J]. Chinese Journal of Catalysis, 2022, 43(11): 2802-2814.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)64022-6

https://www.cjcatal.com/EN/Y2022/V43/I11/2802

Figures/Tables 12

Fig. 1. Schematic illustration of advanced structurally-regulating strategies for metallenes.

Fig. 2. Defects engineered metallenes. RuO2 NSs with multiscales defects: (a) low-magnification HAADF-STEM image; (b) AFM image; (c,d) high-resolution HAADF-STEM images. Reprinted with permission from Ref. [33]. Copyright 2020, Royal Society Chemistry. PtTe2 NSs with corrugated and roughened surface: (e) low-magnification HAADF-STEM image; (f) AFM image; (g) STEM image and corresponding elemental mapping images; (h) atomically-resolved image. Reprinted with permission from Ref. [18]. Copyright 2021, Springer Nature. Porous Pd metallenes: (i) HAADF-STEM image; (j-l) TEM images. Reprinted with permission from Ref. [34]. Copyright 2021, John Wiley and Sons. Perforated Pd NSs: (m,n) TEM images. Reprinted with permission from Ref. [35]. Copyright 2019, John Wiley and Sons. Pd3Pb UPINs: (o) HAADF-STEM; (p) TEM images. Reprinted with permission from Ref. [37]. Copyright 2021, John Wiley and Sons.

Fig. 3. Unconventional-phase Metallenes. Au square NSs on GO sheets: (a) TEM image; (b) HR-TEM image; (c,d) SAED patterns. Reprinted with permission from Ref. [22]. Copyright 2021, Springer Nature. Amorphous Ir NSs: (e) TEM; (f) HAADF-STEM images. Reprinted with permission from Ref. [42]. Copyright 2019, Springer Nature. Amorphous/crystalline hetero-phase Pd NSs: (g) HAADF-STEM image; (h,i) corresponding FFT patterns; (j) SAED pattern; (k) TEM image. Reprinted with permission from Ref. [47]. Copyright 2018, John Wiley and Sons. Amorphous/crystalline hetero-phase PdCu NSs: (l) TEM image; (m) HAADF-STEM image; (n) SAED patterns; (o) HAADF-STEM image of PdCu NSs after aging for 14 days. Reprinted with permission from Ref. [48]. Copyright 2019, Oxford University Press.

Fig. 4. Strain-engineered metallenes. PdMo@Pd bimetallenes: (a,b) HAADF-STEM images; (c) AFM image; (d) atomically-resolved STEM image. Reprinted with permission from Ref. [9]. Copyright 2019, Springer Nature. PtPb core@Pt shell nanoplates: (e) the model of hexagonal nanoplates; (f) HAADF-STEM image from in-plate view; (g) the schematic atom models of hexagonal nanoplates from top and side views. Reprinted with permission from Ref. [54]. Copyright 2016, American Association for the Advancement of Science. Thickness-tuned Pd NSs: (h-j) TEM images; (k) size and thickness distribution; (l-n) high-resolution HAADF-STEM images; (o) the intensity profile and calculated average d-spacing of (111) planes from the NSs in (l) to (n) and Pd nanoparticles. Reprinted with permission from Ref. [55]. Copyright 2019, American Association for the Advancement of Science.

Fig. 5. Interface-engineered metallenes. RuOx-on-Pd NSs: (a) TEM image; (b) HAADF-STEM image; (c) pseudo-color surface plot of HAADF-STEM image; (d,e) HAADF-STEM images of two single NSs from the erect side view. Reprinted with permission from Ref. [58]. Copyright 2021, John Wiley and Sons. SnO2/Pd NSs: (f) TEM image; (g) HRTEM image. Reprinted with permission from Ref. [60]. Copyright 2018, John Wiley and Sons. SnO2/Rh NSs: (h) TEM image; (i) spherical-aberration high-resolution TEM image; (j) schematic illustration of the atomic model of SnO2/Rh NSs. Reprinted with permission from Ref. [61]. Copyright 2020, John Wiley and Sons.

Fig. 6. The doping and alloying-engineered metallenes. RhPdH metallenes: (a,b) HAADF-STEM; (c,d) high-resolution HAADF-STEM images. Reprinted with permission from Ref. [68]. Copyright 2020, American Chemical Society. MoPdH metallenes: (e,f) HAADF-STEM images; HAADF-STEM image with EELS spectra for MoPdH (g) and MoPd (h) metallenes. Reprinted with permission from Ref. [69]. Copyright 2021, American Chemical Society. Co-substituted Ru bimetallene: (i) HAADF-STEM image; (j) AFM image; (k) high-resolution HAADF-STEM image; (l) EDX line scanning profile and EDX mapping. Reprinted with permission from Ref. [70]. Copyright 2018, Springer Nature. PdIr bimetallene: (m) Low-magnification HAADF-STEM image; (n) TEM image; (o) AFM image; (p) high-resolution HAADF-STEM image. Reprinted with permission from Ref. [71]. Copyright 2021, Oxford University Press.

Table 1 Summary of representative metallenes and their applications in electrocatalysis, phototherapy, and organic catalysis.

Material	Phase	Morphology	Thickness	Application	Ref.
Au Bi Bi Co Co Cu MoPdH Pd Pd Pd Pd Pd Pd Pd PdCr PdCu PdCu PdMo PdZn PdCu Pd₃Pb Pd₃Sn Pd₃Cd PdPtAg Pd-RuO₂ Pd-SnO₂ Pd@Ru PtCu PtPb/Pt PtTe₂ Rh Rh Rh RhW RhPdH Rh-SnO₂ Ru RuO₂ RuRh RuMn SA-Co/Ru	2H — rhombohedral hcp hcp fcc fcc fcc fcc fcc fcc fcc fcc a/c fcc fcc fcc fcc fct a/c fcc fcc fcc fcc — — — fcc hcp trigonal — fcc a/c fcc fcc — hcp hcp hcp hcp hcp	NSs NSs NSs NSs NSs NSs NSs NSs NSs porous NSs porous NSs porous NSs porous NSs NSs NSs NSs NSs NSs NSs NSs porous NSs porous NSs porous NSs NSs NSs NSs NSs NSs NSs defect NSs NSs NSs NSs NSs NSs NSs NSs defect NSs NSs NSs NSs	2.4 nm 0.65 nm 1.45 nm 0.84 nm 1.3 nm 5 nm 2.7 nm 3, 5, 8 ML 1.8 nm 0.9 nm 3.3 nm 5 nm 1.5 nm 1.0 nm 1.34 nm 2.8 nm 2.7 nm 0.88 nm 3.0 nm 1.2 nm 2.6 nm 2.6 nm 2.7 nm 3 nm 1.7 nm 4 nm 1.9 nm 1.3 nm 4.5 nm 1.2 nm 0.4 nm 0.9 nm 1.3 nm 1.8 nm 1.8 nm 2.2 nm 1.2 nm 2 nm 1.9 nm 1.1 nm 1.6 nm	— CO₂RR CO₂RR CO₂RR CO₂RR CORR MOR ORR phototherapy ORR EOR, HER phototherapy FAOR organic reaction Sensor FAOR MOR ORR EOR organic reaction ORR ORR ORR EOR ORR CO₂RR organic reaction EOR ORR HER organic reaction organic reaction organic reaction organic reaction HER EOR HER OER Li-CO₂ battery HER, OER HER	[22] [78] [79] [6] [80] [8] [69] [55] [24] [34] [81] [36] [35] [47] [82] [73] [72] [9] [40] [48] [37] [37] [37] [77] [58] [60] [83] [74] [54] [18] [84] [85] [49] [75] [68] [61] [86] [33] [76] [87] [70]

Fig. 7. The metallenes for the ORR. (a-d) The ORR performance of Pd metallenes. Reprinted with permission from Ref. [34]. Copyright 2021, John Wiley and Sons. (e-h) Electrocatalytic performance of PdMo bimetallenes for the ORR. Reprinted with permission from Ref. [9]. Copyright 2019, Springer Nature. (i-l) The ORR performance of RuOx-on-Pd NSs. Reprinted with permission from Ref. [58]. Copyright 2021, John Wiley and Sons.

Fig. 8. The metallenes for the CO2RR. (a-d) CO2RR-to-formate performance of Co NSs. Reprinted with permission from Ref. [6]. Copyright 2019, Springer Nature. (e-h) CO2RR-to-CO performance of Pd NSs with different edge lengths. Reprinted with permission from Ref. [89]. Copyright 2018, John Wiley and Sons. (i-l) CO2RR-to-formate performance of bismuthenes. Reprinted with permission from Ref. [78]. Copyright 2020, Springer Nature.

Fig. 10. The metallenes for the SMOR. (a,b) The MOR performance of MoPdH bimetallene. Reprinted with permission from Ref. [69]. Copyright 2021, American Chemical Society. (c,d) The EOR performance of PdZn with fct phase. Reprinted with permission from Ref. [40]. Copyright 2019, American Chemical Society. (e,f) The FAOR performance of PdCu NSs. Reprinted with permission from Ref. [73].54 Copyright 2017, John Wiley and Sons.

Fig. 11. Perspectives of metallenes for future: the theory-guided design of active metallenes-based electrocatalysts, the identification of active sites and enhancement mechanisms, the universal and large-scale synthesis of metallenes, and the evaluation of metallenes in practical devices.

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