Enhancing the photoelectrochemical performance of p-silicon through TiO₂ coating decorated with mesoporous MoS₂

Abstract

MoS₂ is a promising electrocatalyst for hydrogen evolution reaction and a good candidate for cocatalyst to enhance the photoelectrochemical (PEC) performance of Si-based photoelectrode in aqueous electrolytes. The main challenge lies in the optimization of the microstructure of MoS₂, to improve its catalytic activity and to construct a mechanically and chemically stable cocatalyst/Si photocathode. In this paper, a highly-ordered mesoporous MoS₂ was synthesized and decorated onto a TiO₂ protected p-silicon substrate. An additional TiO₂ necking was introduced to strengthen the bonding between the MoS₂ particles and the TiO₂ layer. This meso-MoS₂/TiO₂/p-Si hybrid photocathode exhibited significantly enhanced PEC performance, where an onset potential of +0.06 V (versus RHE) and a current density of −1.8 mA/cm² at 0 V (versus RHE) with a Faradaic efficiency close to 100% was achieved in 0.5 mol/L H₂SO₄. Additionally, this meso-MoS₂/TiO₂/p-Si photocathode showed an excellent PEC ability and durability in alkaline media. This paper provides a promising strategy to enhance and protect the photocathode through high-performance surface cocatalysts.

Graphical abstract

Keywords

photoelectrocatalysis / hydrogen evolution / Si photocathode / mesoporous MoS₂

References

[1] Strandwitz N C, Turner-Evans D B, Tamboli A C, Photoelectrochemical behavior of planar and microwire-array Si|GaP electrodes. Advanced Energy Materials, 2012, 2(9): 1109–1116

[2] Yue P, She H, Zhang L, Super-hydrophilic CoAl-LDH on BiVO₄ for enhanced photoelectrochemical water oxidation activity. Applied Catalysis B: Environmental, 2021, 286: 119875

[3] Li Y, Yang Y, Huang J, Preparation of CuS/BiVO₄ thin film and its efficacious photoelectrochemical performance in hydrogen generation. Rare Metals, 2019, 38(5): 428–436

[4] Sun K, Shen S, Liang Y, Enabling silicon for solar-fuel production. Chemical Reviews, 2014, 114(17): 8662–8719

[5] Liu D, Ma J, Long R, Silicon nanostructures for solar-driven catalytic applications. Nano Today, 2017, 17: 96–116

[6] Fan R, Zhou J, Xun W, Highly efficient and stable Si photocathode with hierarchical MoS₂/Ni₃S₂ catalyst for solar hydrogen production in alkaline media. Nano Energy, 2020, 71: 104631

[7] Li H, Wang T, Liu S, Controllable distribution of oxygen vacancies in grain boundaries of p-Si/TiO₂ heterojunction photocathodes for solar water splitting. Angewandte Chemie, 2021, 133(8): 4080–4083

[8] Zheng J, Lyu Y, Wang R, Crystalline TiO₂ protective layer with graded oxygen defects for efficient and stable silicon-based photocathode. Nature Communications, 2018, 9(1): 3572

[9] Zhou X, Liu R, Sun K, Interface engineering of the photoelectrochemical performance of Ni-oxide-coated n-Si photoanodes by atomic-layer deposition of ultrathin films of cobalt oxide. Energy & Environmental Science, 2015, 8(9): 2644–2649

[10] Fu Q, Wang W, Yang L, Controllable synthesis of high quality monolayer WS₂ on a SiO₂/Si substrate by chemical vapor deposition. RSC Advances, 2015, 5(21): 15795–15799

[11] Xun W, Wang Y, Fan R, Activating the MoS₂ basal plane toward enhanced solar hydrogen generation via in situ photoelectrochemical control. ACS Energy Letters, 2021, 6(1): 267–276

[12] Fan R, Dong W, Fang L, More than 10% efficiency and one-week stability of Si photocathodes for water splitting by manipulating the loading of the Pt catalyst and TiO₂ protective layer. Journal of Materials Chemistry A, Materials for Energy and Sustainability, 2017, 5(35): 18744–18751

[13] Li F, Yuan Y, Feng X, Coating of phosphide catalysts on p-silicon by a necking strategy for improved photoelectrochemical characteristics in alkaline media. ACS Applied Materials & Interfaces, 2021, 13(17): 20185–20193

[14] Lin H, Li S, Yang G, In situ assembly of MoS_x thin-film through self-reduction on p-Si for drastic enhancement of photoelectrochemical hydrogen evolution. Advanced Functional Materials, 2021, 31(3): 2007071

[15] Seger B, Pedersen T, Laursen A B, Using TiO₂ as a conductive protective layer for photocathodic H₂ evolution. Journal of the American Chemical Society, 2013, 135(3): 1057–1064

[16] Chen C J, Veeramani V, Wu Y H, Phosphorous-doped molybdenum disulfide anchored on silicon as an efficient catalyst for photoelectrochemical hydrogen generation. Applied Catalysis B: Environmental, 2020, 263: 118259

[17] Wang H, Zhang L, Chen Z, Semiconductor heterojunction photocatalysts: design, construction, and photocatalytic performances. Chemical Society Reviews, 2014, 43(15): 5234

[18] Li S, Zhang P, Song X, Photoelectrochemical hydrogen production of TiO₂ passivated Pt/Si-nanowire composite photocathode. ACS Applied Materials & Interfaces, 2015, 7(33): 18560–18565

[19] Fu H, Varadhan P, Tsai M L, Improved performance and stability of photoelectrochemical water-splitting Si system using a bifacial design to decouple light harvesting and electrocatalysis. Nano Energy, 2020, 70: 104478

[20] Zhu L, Lin H, Li Y, A rhodium/silicon co-electrocatalyst design concept to surpass platinum hydrogen evolution activity at high overpotentials. Nature Communications, 2016, 7(1): 12272

[21] Liu J, Wu H, Li F, Recent progress in non-precious metal single atomic catalysts for solar and non-solar driven hydrogen evolution reaction. Advanced Sustainable Systems, 2020, 4(11): 2000151

[22] Hu C, Zhang L, Gong J. Recent progress made in the mechanism comprehension and design of electrocatalysts for alkaline water splitting. Energy & Environmental Science, 2019, 12(9): 2620–2645

[23] Ding Q, Meng F, English C R, Efficient photoelectrochemical hydrogen generation using heterostructures of Si and chemically exfoliated metallic MoS₂. Journal of the American Chemical Society, 2014, 136(24): 8504–8507

[24] Kwon K C, Choi S, Lee J, Drastically enhanced hydrogen evolution activity by 2D to 3D structural transition in anion-engineered molybdenum disulfide thin films for efficient Si-based water splitting photocathodes. Journal of Materials Chemistry A, Materials for Energy and Sustainability, 2017, 5(30): 15534–15542

[25] Wang H, Xiao X, Liu S, Structural and electronic optimization of MoS₂ edges for hydrogen evolution. Journal of the American Chemical Society, 2019, 141(46): 18578–18584

[26] Kiriya D, Lobaccaro P, Nyein H Y Y, General thermal texturization process of MoS₂ for efficient electrocatalytic hydrogen evolution reaction. Nano Letters, 2016, 16(7): 4047–4053

[27] Karunadasa H I, Montalvo E, Sun Y, A molecular MoS₂ edge site mimic for catalytic hydrogen generation. Science, 2012, 335(6069): 698–702

[28] Wang W, Zhu S, Cao Y, Edge-enriched ultrathin MoS₂ embedded yolk-shell TiO₂ with boosted charge transfer for superior photocatalytic H₂ evolution. Advanced Functional Materials, 2019, 29(36): 1901958

[29] Kibsgaard J, Chen Z, Reinecke B N, Engineering the surface structure of MoS₂ to preferentially expose active edge sites for electrocatalysis. Nature Materials, 2012, 11(11): 963–969

[30] Li X, Li Y, Wang H, Fabrication of a three-dimensional bionic Si/TiO₂/MoS₂ photoelectrode for efficient solar water splitting. ACS Applied Energy Materials, 2021, 4(1): 730–736

[31] Li F, Wang C, Han X, Confinement effect of mesopores: in situ synthesis of cationic tungsten-vacancies for a highly ordered mesoporous tungsten phosphide electrocatalyst. ACS Applied Materials & Interfaces, 2020, 12(20): 22741–22750

[32] Rasamani K D, Alimohammadi F, Sun Y. Interlayer-expanded MoS₂. Materials Today, 2017, 20(2): 83–91

[33] Tsai C, Abild-Pedersen F, Nørskov J K. Tuning the MoS₂ edge-site activity for hydrogen evolution via support interactions. Nano Letters, 2014, 14(3): 1381–1387

[34] Fan R, Mao J, Yin Z, Efficient and stable silicon photocathodes coated with vertically standing nano-MoS₂ films for solar hydrogen production. ACS Applied Materials & Interfaces, 2017, 9(7): 6123–6129

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