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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Grant Nos. 51672174, 51779139, 51772190, and 51972210) and the Advanced Energy Material and Technology Center of Shanghai Jiao Tong University, China.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11708-021-0783-7 and is accessible for authorized users.

RIGHTS & PERMISSIONS

2021 Higher Education Press