Unsaturated bi-heterometal clusters in metal-vacancy sites of 2D MoS₂ for efficient hydrogen evolution

Abstract

The valence states and coordination structures of doped heterometal atoms in two-dimensional (2D) nanomaterials lack predictable regulation strategies. Hence, a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism, which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide. The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites. Among them, the strong binding energy of negatively charged suspended S and O sites for H⁺, as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*, reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation. Whereupon, the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec⁻¹. In brief, this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.

Keywords

clusters / hydrogen evolution reaction / metal vacancy / MoS₂ / unsaturated heterometal

References

[1] Li H, Tsai C, Koh AL, et al. Activating and optimizing MoS₂ basal planes for hydrogen evolution through the formation of strained sulphur vacancies. Nat Mater. 2016; 15 (1): 48- 53.

[2] Shi Y, Zhou Y, Yang D-R, et al. Energy level engineering of MoS₂ by transition-metal doping for accelerating hydrogen evolution reaction. J Am Chem Soc. 2017; 139 (43): 15479- 15485.

[3] Jiang J, Xu T, Lu J, Sun L, Ni Z. Defect engineering in 2D materials: precise manipulation and improved functionalities. Research. 2019; 2019: 4641739.

[4] Zhao X, Ji Y, Chen J, et al. Healing of planar defects in 2D materials via grain boundary sliding. Adv Mater. 2019; 31 (16): 1900237.

[5] Joyner J, Oliveira EF, Yamaguchi H, et al. Graphene supported MoS₂ structures with high defect density for an efficient HER electrocatalysts. ACS Appl Mater Interfaces. 2020; 12 (11): 12629- 12638.

[6] Liu L, Wu J, Wu L, et al. Phase-selective synthesis of 1T' MoS₂ monolayers and heterophase bilayers. Nat Mater. 2018; 17 (12): 1108- 1114.

[7] Tan C, Luo Z, Chaturvedi A, et al. Preparation of high-percentage 1T-phase transition metal dichalcogenide nanodots for electrochemical hydrogen evolution. Adv Mater. 2018; 30 (9): 1705509.

[8] Xiong Q, Wang Y, Liu P-F, et al. Cobalt covalent doping in MoS₂ to induce bifunctionality of overall water splitting. Adv Mater. 2018; 30 (29): 1801450.

[9] Yang S-Z, Gong Y, Manchanda P, et al. Rhenium-doped and stabilized MoS₂ atomic layers with basal-plane catalytic activity. Adv Mater. 2018; 30 (51): 1803477.

[10] Kim M, Anjum MAR, Lee M, Lee BJ, Lee JS. Activating MoS₂ basal plane with Ni₂P nanoparticles for Pt-like hydrogen evolution reaction in acidic media. Adv Funct Mater. 2019; 29 (10): 1809151.

[11] Zhang X, Zhou F, Zhang S, Liang Y, Wang R. Engineering MoS₂ basal planes for hydrogen evolution via synergistic ruthenium doping and nanocarbon hybridization. Adv Sci. 2019; 6 (10): 1900090.

[12] Park Y, Shin S, An Y, et al. Tunable optical transition in 2H-MoS₂ via direct electrochemical engineering of vacancy defects and surface S-C bonds. ACS Appl Mater Interfaces. 2020; 12 (36): 40870- 40878.

[13] Shao G, Xue X-X, Wu B, et al. Template-assisted synthesis of metallic 1T'-Sn_0.3W_0.7S₂ nanosheets for hydrogen evolution reaction. Adv Funct Mater. 2020; 30 (5): 1906069.

[14] Zou J, Cai Z, Lai Y, et al. Doping concentration modulation in vanadium-doped monolayer molybdenum disulfide for synaptic transistors. ACS Nano. 2021; 15 (4): 7340- 7347.

[15] Liu L, Ye K, Lin C, et al. Grain-boundary-rich polycrystalline monolayer WS₂ film for attomolar-level Hg²⁺ sensors. Nat Commun. 2021; 12: 3870.

[16] Wang X, Zhang Y, Si H, et al. Single-atom vacancy defect to trigger high-efficiency hydrogen evolution of MoS₂. J Am Chem Soc. 2020; 142 (9): 4298- 4308.

[17] Li L, Qin Z, Ries L, et al. Role of sulfur vacancies and undercoordinated mo regions in MoS₂ nanosheets toward the evolution of hydrogen. ACS Nano. 2019; 13 (6): 6824- 6834.

[18] Yang Q, Liu H, Yuan P, et al. Single carbon vacancy traps atomic platinum for hydrogen evolution catalysis. J Am Chem Soc. 2022; 144 (5): 2171- 2178.

[19] Zhang J, Zhao Y, Guo X, et al. Single platinum atoms immobilized on an MXene as an efficient catalyst for the hydrogen evolution reaction. Nat Catal. 2018; 1 (12): 985- 992.

[20] Zhang Z, Feng C, Wang D, et al. Selectively anchoring single atoms on specific sites of supports for improved oxygen evolution. Nat Commun. 2022; 13: 2473.

[21] Ge J, Zhang D, Qin Y, et al. Dual-metallic single Ru and Ni atoms decoration of MoS₂ for high-efficiency hydrogen production. Appl Catal B. 2021; 298 (5): 120557.

[22] Luo Z, Ouyang Y, Zhang H, et al. Chemically activating MoS₂ via spontaneous atomic palladium interfacial doping towards efficient hydrogen evolution. Nat Commun. 2018; 9: 2120.

[23] Zhou Y, Zhang J, Song E, et al. Enhanced performance of in-plane transition metal dichalcogenides monolayers by configuring local atomic structures. Nat Commun. 2020; 11: 2253.

[24] Guo Y, Wang M, Zhu Q, Xiao D, Ma D. Ensemble effect for single-atom, small cluster and nanoparticle catalysts. Nat Catal. 2022; 5 (9): 766- 776.

[25] Xu J, Shao G, Tang X, et al. Frenkel-defected monolayer MoS₂ catalysts for efficient hydrogen evolution. Nat Commun. 2022; 13: 2193.

[26] Shao G, Xiang H, Huang M, et al. S vacancies in 2D SnS₂ accelerating hydrogen evolution reaction. Sci China Mater. 2022; 65 (7): 1833- 1841.

[27] Yu Q, Zhang Z, Qiu S, et al. A Ta-TaS₂ monolith catalyst with robust and metallic interface for superior hydrogen evolution. Nat Commun. 2021; 12: 6051.

[28] Ye G, Gong Y, Lin J, et al. Defects engineered monolayer MoS₂ for improved hydrogen evolution reaction. Nano Lett. 2016; 16 (2): 1097- 1103.

[29] Hus SM, Ge R, Chen P-A, et al. Observation of single-defect memristor in an MoS₂ atomic sheet. Nat Nanotechnol. 2021; 16 (1): 58- 62.

[30] Choi W, Kim J, Lee E, Mehta G, Prasad V. Asymmetric 2D MoS₂ for scalable and high-performance piezoelectric sensors. ACS Appl Mater Interfaces. 2021; 13 (11): 13596- 13603.

[31] Shao G, Lu Y, Hong J, et al. Seamlessly splicing metallic Sn_xMo_1-xS₂ at MoS₂ edge for enhanced photoelectrocatalytic performance in microreactor. Adv Sci. 2020; 7 (24): 2002172.

[32] Fujisawa K, Carvalho BR, Zhang T, et al. Quantification and healing of defects in atomically thin molybdenum disulfide: beyond the controlled creation of atomic defects. ACS Nano. 2021; 15 (6): 9658- 9669.

[33] Li J, Kang J, Cai Q, et al. Boosting hydrogen evolution performance of MoS₂ by band structure engineering. Adv Mater Interfaces. 2017; 4 (16): 1700303.

[34] Cai L, He J, Liu Q, et al. Vacancy-induced ferromagnetism of MoS₂ nanosheets. J Am Chem Soc. 2015; 137 (7): 2622- 2627.

[35] Hong J, Jin C, Yuan J, Zhang Z. Atomic defects in two-dimensional materials: from single-atom spectroscopy to functionalities in opto-/electronics, nanomagnetism, and catalysis. Adv Mater. 2017; 29 (14): 1606434.

[36] Li Y, Gu Q, Johannessen B, et al. Synergistic Pt doping and phase conversion engineering in two-dimensional MoS₂ for efficient hydrogen evolution. Nano Energy. 2021; 84: 105898.

[37] Hu D, Zhao T, Ping X, et al. Unveiling the layer-dependent catalytic activity of PtSe₂ atomic crystals for the hydrogen evolution reaction. Angew Chem Int Ed. 2019; 58 (21): 6977- 6981.

[38] Fan H, Wu R, Liu H, Yang X, Sun Y, Chen C. Synthesis of metal-phase-assisted 1T@2H-MoS₂ nanosheet-coated black TiO₂ spheres with visible light photocatalytic activities. J Mater Sci. 2018; 53 (14): 10302- 10312.

[39] Alam MJ, Murkute P, Sushama S, et al. Room-temperature ultraviolet-ozone annealing of ZnO and ZnMgO nanorods to attain enhanced optical properties. J Mater Sci Mater Electron. 2020; 31 (21): 18777- 18790.

[40] Pawlak DA, Ito M, Oku M, Shimamura K, Fukuda T. Interpretation of XPS (O 1s) in mixed oxides proved on mixed perovskite crystals. J Phys Chem B. 2002; 106 (2): 504- 507.

[41] Guo H, Sun Y, Zhai P, et al. Swift-heavy ion irradiation-induced latent tracks in few- and mono-layer MoS₂. Appl Phys A. 2016; 122 (4): 375.

[42] Luo Z, Zhang H, Yang Y, et al. Reactant friendly hydrogen evolution interface based on di-anionic MoS₂ surface. Nat Commun. 2020; 11: 1116.

[43] Zhang X, Chen A, Chen L, Zhou Z. 2D materials bridging experiments and computations for electro/photocatalysis. Adv Energy Mater. 2022; 12 (4): 2003841.

[44] Xue H, Meng A, Chen C, Xue H, Li Z, Wang C. Phosphorus-doped MoS₂ with sulfur vacancy defects for enhanced electrochemical water splitting. Sci China Mater. 2022; 65 (3): 712- 720.

[45] Daelman N, Capdevila-Cortada M, López N. Dynamic charge and oxidation state of Pt/CeO₂ single-atom catalysts. Nat Mater. 2019; 18 (11): 1215- 1221.

[46] Lang R, Xi W, Liu J-C, et al. Non defect-stabilized thermally stable single-atom catalyst. Nat Commun. 2019; 10 (1): 234.

[47] Wei H, Liu X, Wang A, et al. FeO_x-supported platinum single-atom and pseudo-single-atom catalysts for chemoselective hydrogenation of functionalized nitroarenes. Nat Commun. 2014; 5: 5634.

[48] Liu K, Zhao X, Ren G, et al. Strong metal-support interaction promoted scalable production of thermally stable single-atom catalysts. Nat Commun. 2020; 11: 1263.

[49] Yang J, Li W, Wang D, Li Y. Electronic metal-support interaction of single-atom catalysts and applications in electrocatalysis. Adv Mater. 2020; 32 (49): 2003300.

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