Assembly of Al-oxo porphyrin frameworks on Si nanowire for enhanced photoelectrocatalytic hydrogen evolution

Abstract

The utilization of solar energy for hydrogen production via water splitting has garnered considerable attention in the realm of renewable energy. Si nanowires photocathodes own the advantages of effective photon absorption, non-toxicity and industrial applicability. Nevertheless, the photoelectrocatalytic (PEC) performance of Si nanowires photocathodes is still limited by ineffective or deficient active sites on their surfaces. Here, we develop an efficient Si-based photocathode modified with Al-porphyrin-based MOF (Al-PMOF), consisted of an earth-abundant metal-containing Al(OH)O₄ cluster bridged by 5, 10, 15, 20-tetrakis(4-carboxyphenyl) porphyrin. The assembled Al-PMOF significantly enhances the photocurrent density of bare Si nanowires photocathodes, resulting in a twofold increase under equivalent conditions, alongside a positive shift of 200 mV in the onset potential of the Si/Al-PMOF photocathode. The improved PEC hydrogen evolution performance is ascribed to accelerate surface charge transfer of Si photocathode and provision of favorable active site for the hydrogen evolution reaction. This work provides insights into the fabrication of semiconductor/molecule catalyst hybrid photocathodes, thus facilitating the realization of high-efficiency PEC water splitting.

References

[1] Chen X-b, Shen S-h, Guo L-j, et al.. Semiconductor-based photocatalytic hydrogen generation [J]. Chemical Reviews, 2010, 110(11): 6503-6570.

[2] Cook T R, Dogutan D K, Reece S Y, et al.. Solar energy supply and storage for the legacy and nonlegacy worlds [J]. Chemical Reviews, 2010, 110(11): 6474-6502.

[3] Wen P, Sun Y-h, Li H, et al.. A highly active three-dimensional Z-scheme ZnO/Au/g-C₃N₄ photocathode for efficient photoelectrochemical water splitting [J]. Applied Catalysis B: Environmental, 2020, 263: 118180.

[4] Khaselev O, Turner J A. A monolithic photovoltaic-photoelectrochemical device for hydrogen production via water splitting [J]. Science, 1998, 280(5362): 425-427.

[5] Zeng G-s, Pham T A, Vanka S, et al.. Development of a photoelectrochemically self-improving Si/GaN photocathode for efficient and durable H₂ production [J]. Nature Materials, 2021, 20(8): 1130-1135.

[6] Tang Y-q, Jiang D, Wang H, et al.. Band gap modulation of nanostructured WO₃ nanoplate film by Ti doping for enhanced photoelectrochemical performance [J]. Journal of Central South University, 2022, 29(9): 2968-2979.

[7] Qi Y-z, Shen Y-b, Zhao S-k, et al.. Dual-loading strategy to construct Au-BiOBr⁻TiO₂ photocatalysts for fast and efficient degradation of xanthates under visible light [J]. Journal of Central South University, 2023, 30(10): 3289-3302.

[8] Chen K-y, Wang R-l, Mei Q, et al.. Spinel-covered interlayer MgO enhances the performance of BiVO4 photocatalytic ammonia synthesis [J]. Applied Catalysis B: Environment and Energy, 2024, 344: 123670.

[9] Wei X-x, Zhang J, Wang L, et al.. Superhydrophilic BiVO₄/MgO/FeCo₂O₄ charge migration achieves efficient photoelectrochemical performance [J]. Chemical Engineering Journal, 2024, 482: 149114.

[10] Tang Y-q, Jiang D, Wang H, et al.. Band gap modulation of nanostructured WO₃ nanoplate film by Ti doping for enhanced photoelectrochemical performance [J]. Journal of Central South University, 2022, 29(9): 2968-2979.

[11] Ye S, Shi W-w, Liu Y, et al.. Unassisted photoelectrochemical cell with multimediator modulation for solar water splitting exceeding 4% solar-to-hydrogen efficiency [J]. Journal of the American Chemical Society, 2021, 143(32): 12499-12508.

[12] Zhou X, Fu B-h, Li L-j, et al.. Hydrogen-substituted graphdiyne encapsulated cuprous oxide photocathode for efficient and stable photoelectrochemical water reduction [J]. Nature Communications, 2022, 13(1): 5770.

[13] Xing H-y, Lei E, Guo Z-g, et al.. Enhancement in the charge transport and photocorrosion stability of CuO photocathode: The synergistic effect of spatially separated dual-cocatalysts and p-n heterojunction [J]. Chemical Engineering Journal, 2020, 394: 124907.

[14] Pati P B, Wang R-w, Boutin E, et al.. Photocathode functionalized with a molecular cobalt catalyst for selective carbon dioxide reduction in water [J]. Nature Communications, 2020, 11(1): 3499.

[15] Li Y, Wang K, Huang D-w, et al.. Cd_xZn_1−xS/Sb₂Se₃ thin film photocathode for efficient solar water splitting [J]. Applied Catalysis B: Environmental, 2021, 286: 119872.

[16] Gu J, Aguiar J A, Ferrere S, et al.. A graded catalytic-protective layer for an efficient and stable watersplitting photocathode [J]. Nature Energy, 2017, 2(2): 16192.

[17] Kim J H, Seo S, Lee J H, et al.. Efficient and stable perovskite-based photocathode for photoelectrochemical hydrogen production [J]. Advanced Functional Materials, 2021, 31(17): 2008277.

[18] Jun S E, Hong S P, Choi S, et al.. Boosting unassisted alkaline solar water splitting using silicon photocathode with TiO₂ nanorods decorated by edge-rich MoS₂ nanoplates [J]. Small, 2021, 17(39): e2103457.

[19] Wu B, Wang T, Liu B, et al.. Stable solar water splitting with wettable organic-layer-protected silicon photocathodes [J]. Nature Communications, 2022, 13: 4460.

[20] Mei Z-w, Chen Y-j, Tong S-f, et al.. Highperformance Si photocathode enabled by spatial decoupling multifunctional layers for water splitting [J]. Advanced Functional Materials, 2022, 32(2): 2107164.

[21] Kang J-h, He W-h, Wang K-k, et al.. Single-atom nickel sites boosting Si nanowires for photoelectrocatalytic CO₂ conversion with nearly 100% selectivity [J]. Chemical Communications, 2024, 60(47): 6039-6042.

[22] Sun X-r, Liu C, Zhang P-l, et al.. Interface-engineered silicon photocathodes with a NiCoP catalyst-modified TiO₂ nanorod array outlayer for photoelectrochemical hydrogen production in alkaline solution [J]. Journal of Power Sources, 2021, 484: 229272.

[23] Pan L-f, Liu Y-h, Yao L, et al.. Cu₂O photocathodes with band-tail states assisted hole transport for standalone solar water splitting [J]. Nature Communications, 2020, 11(1): 318.

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

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

[26] Pan L-f, Kim J H, Mayer M T, et al.. Boosting the performance of Cu₂O photocathodes for unassisted solar water splitting devices [J]. Nature Catalysis, 2018, 1: 412-420.

[27] Li H, Liu B, Feng S-j, et al.. Construction of uniform buried pn junctions on pyramid Si photocathodes using a facile and safe spin-on method for photoelectrochemical water splitting [J]. Journal of Materials Chemistry A, 2020, 8(1): 224-230.

[28] Wang K-k, Liu Y, Kang J-h, et al.. Site-selective photocoupled electrocatalytic CO₂ reduction over efficient Al-oxo chain based-porphyrin framework [J]. Applied Catalysis B: Environmental, 2023, 325: 122315.

[29] Fateeva A, Chater P A, Ireland C P, et al.. A water-stable porphyrin-based metal-organic framework active for visible-light photocatalysis [J]. Angewandte Chemie, 2012, 124(30): 7558-7562.

[30] Sadeghi N, Sharifnia S, Do T O. Enhanced CO₂ photoreduction by a graphene-porphyrin metal-organic framework under visible light irradiation [J]. Journal of Materials Chemistry A, 2018, 6(37): 18031-18035.

[31] Lee D T, Jamir J D, Peterson G W, et al.. Protective fabrics: Metal-organic framework textiles for rapid photocatalytic sulfur mustard simulant detoxification [J]. Matter, 2020, 2(2): 404-415.

[32] Boyd P G, Chidambaram A, García-Díez E, et al.. Data-driven design of metal-organic frameworks for wet flue gas CO₂ capture [J]. Nature, 2019, 576: 253-256.

[33] Ma W-c, Xie M-c, Xie S-j, et al.. Nickel and indium core-shell co-catalysts loaded silicon nanowire arrays for efficient photoelectrocatalytic reduction of CO₂ to formate [J]. Journal of Energy Chemistry, 2021, 54: 422-428.

[34] Roy K, Ghosh D, Sarkar K, et al.. Chlorophyll(a)/carbon quantum dot bio-nanocomposite activated nano-structured silicon as an efficient photocathode for photoelectrochemical water splitting [J]. ACS Applied Materials & Interfaces, 2020, 12(33): 37218-37226.

[35] Sadeghi N, Sharifnia S, Do T O. Enhanced CO₂ photoreduction by a graphene - porphyrin metal-organic framework under visible light irradiation [J]. Journal of Materials Chemistry A, 2018, 6(37): 18031-18035.

[36] Zhong M, Hisatomi T, Kuang Y-b, et al.. Surface modification of CoO_x loaded BiVO₄ photoanodes with ultrathin p-type NiO layers for improved solar water oxidation [J]. Journal of the American Chemical Society, 2015, 137(15): 5053-5060.

[37] Wang L-n, Liu Z-j, Zhang J-m, et al.. Boosting charge separation of BiVO₄ photoanode modified with 2D metal-organic frameworks nanosheets for high-performance photoelectrochemical water splitting [J]. Chinese Chemical Letters, 2023, 34(6): 108007.

[38] Jia Y-j, Tian Z-h, Gao J-yu. An effective integrated Cu₂O photocathode to boost photoelectrocatalytic CO₂ conversion [J]. Journal of Materials Chemistry A, 2023, 11(21): 11411-11425.

[39] Murugan C, Mary A S, Velmurugan R, et al.. Investigating the interfacial charge transfer between electrodeposited BiVO₄ and pulsed laser-deposited Co₃O₄ p-n junction photoanode in photoelectrocatalytic water splitting [J]. Chemical Engineering Journal, 2024, 483: 149104.

[40] Poli I, Hintermair U, Regue M, et al.. Graphite-protected CsPbBr₃ perovskite photoanodes functionalised with water oxidation catalyst for oxygen evolution in water [J]. Nature Communications, 2019, 10(1): 2097.

[41] Kamimura J, Bogdanoff P, Ramsteiner M, et al.. P-type doping of GaN nanowires characterized by photoelectrochemical measurements [J]. Nano Letters, 2017, 17(3): 1529-1537.

[42] Lin Y-j, Xu Y, Mayer M T, et al.. Growth of p-type hematite by atomic layer deposition and its utilization for improved solar water splitting [J]. Journal of the American Chemical Society, 2012, 134(12): 5508-5511.

[43] Duchene J S, Tagliabue G, Welch A J, et al.. Hot hole collection and photoelectrochemical CO₂ reduction with plasmonic Au/p-GaN photocathodes [J]. Nano Letters, 2018, 18(4): 2545-2550.

[44] Xiao J-r, Huang H-l, Huang Q-y, et al.. Remarkable improvement of the turn - on characteristics of a Fe₂O₃ photoanode for photoelectrochemical water splitting with coating a FeCoW oxy - hydroxide gel [J]. Applied Catalysis B: Environmental, 2017, 212: 89-96.

[45] Ponomarev E A, Peter L M. A generalized theory of intensity modulated photocurrent spectroscopy (IMPS) [J]. Journal of Electroanalytical Chemistry, 1995, 396(1–2): 219-226.

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