Abstract
Vertically aligned p-silicon nanowire (SiNW) arrays have been extensively investigated in recent years as promising photocathodes for solar-driven hydrogen evolution. However, the fabrication of SiNW photocathodes with both high photoelectrocatalytic activity and long-term operational stability using a simple and affordable approach is a challenging task. Herein, we report conformal and continuous deposition of a di-cobalt phosphide (Co2P) layer on lithography-patterned highly ordered SiNW arrays via a cost-effective drop-casting method followed by a low-temperature phosphorization treatment. The as-deposited Co2P layer consists of crystalline nanoparticles and has an intimate contact with SiNWs, forming a well-defined SiNW@Co2P core/shell nanostructure. The conformal and continuous Co2P layer functions as a highly efficient catalyst capable of substantially improving the photoelectrocatalytic activity for the hydrogen evolution reaction (HER) and effectively passivates the SiNWs to protect them from photo-oxidation, thus prolonging the lifetime of the electrode. As aconsequence, the SiNW@Co2P photocathode with an optimized Co2P layer thickness exhibits a high photocurrent density of–21.9 mA·cm−2 at 0 V versus reversible hydrogen electrode and excellent operational stability up to 20 h for solar-driven hydrogen evolution, outperforming many nanostructured silicon photocathodes reported in the literature. The combination of passivation and catalytic functions in a single continuous layer represents a promising strategy for designing high-performance semiconductor photoelectrodes for use insolar-driven water splitting, which may simplify fabrication procedures andpotentially reduce production costs.
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References
Dincer, I. Renewable energy and sustainable development: A crucial review. Renew. Sust. Energ. Rev.2000, 4, 157–175.
Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.; Mi, Q. X.; Santori, E. A.; Lewis, N. S. Solar water splitting cells. Chem. Rev.2010, 110, 6446–6473.
Cook, T. R.; Dogutan, D. K.; Reece, S. Y.; Surendranath, Y.; Teets, T. S.; Nocera, D. G. Solar energy supply and storage for the legacy and nonlegacy worlds. Chem. Rev.2010, 110, 6474–6502.
Lewis, N. S.; Nocera, D. G. Powering the planet: Chemical challenges in solar energy utilization. Proc. Natl. Acad. Sci. USA2006, 103, 15729–15735.
Reece, S. Y.; Hamel, J. A.; Sung, K.; Jarvi, T. D.; Esswein, A. J.; Pijpers, J. J. H.; Nocera, D. G. Wireless solar water splitting using silicon-based semiconductors and earth-abundant catalysts. Science2011, 334, 645–648.
Sun, K.; Shen, S. H.; Liang, Y. Q.; Burrows, P. E.; Mao, S. S.; Wang, D. L. Enabling silicon for solar-fuel production. Chem. Rev.2014, 114, 8662–8719.
Candea, R. M.; Kastner, M.; Goodman, R.; Hickok, N. Photoelectrolysis of water-Si in salt-water. J. Appl. Phys.1976, 47, 2724–2726.
Thalluri, S. M.; Borme, J.; Xiong, D. H.; Xu, J. Y.; Li, W.; Amorim, I.; Alpuim, P.; Gaspar, J.; Fonseca, H.; Qiao, L. et al. Highly-ordered silicon nanowire arrays for photoelectrochemical hydrogen evolution: An investigation on the effect of wire diameter, length and inter-wire spacing. Sustainable Energy Fuels2018. DOI: 10.1039/C7SE00591A.
Bao, X. Q.; Petrovykh, D. Y.; Alpuim, P.; Stroppa, D. G.; Guldris, N.; Fonseca, H.; Costa, M.; Gaspar, J.; Jin, C. H.; Liu, L. F. Amorphous oxygen-rich molybdenum oxysulfide decorated p-type silicon microwire arrays for efficient photoelectrochemical water reduction. Nano Energy2015, 16, 130–142.
Yuhas, B. D.; Smeigh, A. L.; Samuel, A. P. S.; Shim, Y.; Bag, S.; Douvalis, A. P.; Wasielewski, M. R.; Kanatzidis, M. G. Biomimetic multifunctional porous chalcogels as solar fuel catalysts. J. Am. Chem. Soc.2011, 133, 7252–7255.
Wang, J.; Zhong, H. X.; Wang, Z. L.; Meng, F. L.; Zhang, X. B. Integrated three-dimensional carbon paper/carbon tubes/cobalt-sulfide sheets as an efficient electrode for overall water splitting. ACS Nano2016, 10, 2342–2348.
Gholamvand, Z.; McAteer, D.; Backes, C.; McEvoy, N.; Harvey, A.; Berner, N. C.; Hanlon, D.; Bradley, C.; Godwin, I.; Rovetta, A. et al. Comparison of liquid exfoliated transition metal dichalcogenides reveals MoSe2 to be the most effective hydrogen evolution catalyst. Nanoscale2016, 8, 5737–5749.
Zhang, L. M.; Liu, C.; Wong, A. B.; Resasco, J.; Yang, P. D. MoS2-wrapped silicon nanowires for photoelectrochemical water reduction. Nano Res.2015, 8, 281–287.
Xiong, D. H.; Zhang, Q. Q.; Thalluri, S. M.; Xu, J. Y.; Li, W.; Fu, X. L.; Liu, L. F. One-step fabrication of monolithic electrodes comprising Co9S8 particles supported on cobalt foam for efficient and durable oxygen evolution reaction. Chem.-Eur. J.2017, 23, 8749–8755.
Chen, C. J.; Yang, K. C.; Basu, M.; Lu, T. H.; Lu, Y. R.; Dong, C. L.; Hu, S. F.; Liu, R. S. Wide range pH-tolerable silicon@pyrite cobalt dichalcogenide microwire array photoelectrodes for solar hydrogen evolution. ACS Appl. Mater. Interfaces2016, 8, 5400–5407.
Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S. The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis. J. Power Sources2017, 366, 105–114.
Wang, H. M.; Naghadeh, S. B.; Li, C. H.; Ying, L.; Allen, A. L.; Zhang, J. Z. Enhanced photoelectrochemical and photocatalytic activities of CdS nanowires by surface modification with MoS2 nanosheets. Sci. China Mater.2018. DOI: 10.1007/s40843-017-9172-x.
Ma, X. Y.; Li, J. Q.; An, C. H.; Feng, J.; Chi, Y. X.; Liu, J. X.; Zhang, J.; Sun, Y. G. Ultrathin Co(Ni)-doped MoS2 nanosheets as catalytic promoters enabling efficient solar hydrogen production. Nano Res.2016, 9, 2284–2293.
Popczun, E. J.; McKone, J. R.; Read, C. G.; Biacchi, A. J.; Wiltrout, A. M.; Lewis, N. S.; Schaak, R. E. Nanostructured nickel phosphide as an electrocatalyst for the hydrogen evolution reaction. J. Am. Chem. Soc.2013, 135, 9267–9270.
Wang, X. G.; Kolen’ko, Y. V.; Bao, X. Q.; Kovnir, K.; Liu, L. F. One-step synthesis of self-supported nickel phosphide nanosheet array cathodes for efficient electrocatalytic hydrogen generation. Angew. Chem., Int. Ed.2015, 54, 8188–8192.
Roske, C. W.; Popczun, E. J.; Seger, B.; Read, C. G.; Pedersen, T.; Hansen, O.; Vesborg, P. C. K.; Brunschwig, B. S.; Schaak, R. E.; Chorkendorff, I. et al. Comparison of the performance of CoP-coated and Pt-coated radial junction n+p-silicon microwire-array photocathodes for the sunlight-driven reduction of water to H2(g). J. Phys. Chem. Lett.2015, 6, 1679–1683.
Bao, X. Q.; Cerqueira, M. F.; Alpuim, P.; Liu, L. F. Silicon nanowire arrays coupled with cobalt phosphide spheres as low-cost photocathodes for efficient solar hydrogen evolution. Chem. Commun.2015, 51, 10742–10745.
Hellstern, T. R.; Benck, J. D.; Kibsgaard, J.; Hahn, C.; Jaramillo, T. F. Engineering cobalt phosphide (CoP) thin film catalysts for enhanced hydrogen evolution activity on silicon photocathodes. Adv. Energy Mater.2016, 6, 1501758.
Wang, X. G.; Li, W.; Xiong, D. H.; Petrovykh, D. Y.; Liu, L. F. Bifunctional nickel phosphide nanocatalysts supported on carbon fiber paper for highly efficient and stable overall water splitting. Adv. Funct. Mater.2016, 26, 4067–4077.
Li, W.; Gao, X. F.; Wang, X. G.; Xiong, D. H.; Huang, P. P.; Song, W. G.; Bao, X. Q.; Liu, L. F. From water reduction to oxidation: Janus Co-Ni-P nanowires as high-efficiency and ultrastable electrocatalysts for over 3,000 h water splitting. J. Power Sources2016, 330, 156–166.
Zhang, Y. T.; Chao, S. J.; Wang, X. B.; Han, H. J.; Bai, Z. Y.; Yang, L. Hierarchical Co9S8 hollow microspheres as multifunctional electrocatalysts for oxygen reduction, oxygen evolution and hydrogen evolution reactions. Electrochim. Acta2017, 246, 380–390.
Li, W.; Xiong, D. H.; Gao, X. F.; Song, W. G.; Xia, F.; Liu, L. F. Self-supported Co-Ni-P ternary nanowire electrodes for highly efficient and stable electrocatalytic hydrogen evolution in acidic solution. Catal. Today2017, 287, 122–129.
Wu, H. B.; Xia, B. Y.; Yu, L.; Yu, X. Y.; Lou, X. W. Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production. Nat. Commun.2015, 6, 6512.
Ma, B. J.; Xu, H. J.; Lin, K. Y.; Li, J.; Zhan, H. J.; Liu, W. Y.; Li, C. Mo2C as non-noble metal Co-catalyst in Mo2C/CdS composite for enhanced photocatalytic H2 evolution under visible light irradiation. ChemSusChem2016, 9, 820–824.
Gong, Q. F.; Wang, Y.; Hu, Q.; Zhou, J. G.; Feng, R. F.; Duchesne, P. N.; Zhang, P.; Chen, F. J.; Han, N.; Li, Y. F. et al. Ultrasmall and phase-pure W2C nanoparticles for efficient electrocatalytic and photoelectrochemical hydrogen evolution. Nat. Commun.2016, 7, 13216.
Yang, Y.; Wang, M.; Zhang, P. L.; Wang, W. H.; Han, H. X.; Sun, L. C. Evident enhancement of photoelectrochemical hydrogen production by electroless deposition of M-B (M = Ni, Co) catalysts on silicon nanowire arrays. ACS Appl. Mater. Interfaces2016, 8, 30143–30151.
Vrubel, H.; Hu, X. L. Molybdenum boride and carbide catalyze hydrogen evolution in both acidic and basic solutions. Angew. Chem., Int. Ed.2012, 51, 12703–12706.
Shalom, M.; Ressnig, D.; Yang, X. F.; Clavel, G.; Fellinger, T. P.; Antonietti, M. Nickel nitride as an efficient electrocatalyst for water splitting. J. Mater. Chem. A2015, 3, 8171–8177.
Bae, D.; Seger, B.; Vesborg, P. C. K.; Hansen, O.; Chorkendorff, I. Strategies for stable water splitting via protected photoelectrodes. Chem. Soc. Rev.2017, 46, 1933–1954.
Chandrasekaran, S.; Nann, T.; Voelcker, N. H. Nanostructured silicon photoelectrodes for solar water electrolysis. Nano Energy2015, 17, 308–322.
Dalchiele, E. A.; Martin, F.; Leinen, D.; Marotti, R. E.; Ramos-Barrado, J. R. Single-crystalline silicon nanowire array-based photoelectrochemical cells. J. Electrochem. Soc.2009, 156, K77–K81.
Jung, J. Y.; Choi, M. J.; Zhou, K. Y.; Li, X. P.; Jee, S. W.; Um, H. D.; Park, M. J.; Park, K. T.; Bang, J. H.; Lee, J. H. Photoelectrochemical water splitting employing a tapered silicon nanohole array. J. Mater. Chem. A2014, 2, 833–842.
Zhang, B. C.; Wang, H.; He, L.; Duan, C. Y.; Li, F.; Ou, X. M.; Sun, B. Q.; Zhang, X. H. The diameter-dependent photoelectrochemical performance of silicon nanowires. Chem. Commun.2016, 52, 1369–1372.
Sim, U.; Jeong, H. Y.; Yang, T. Y.; Nam, K. T. Nanostructural dependence of hydrogen production in silicon photocathodes. J. Mater. Chem. A2013, 1, 5414–5422.
Bazri, B.; Lin, Y. C.; Lu, T. H.; Chen, C. J.; Kowsari, E.; Hu, S. F.; Liu, R. S. A heteroelectrode structure for solar water splitting: Integrated cobalt ditelluride across a TiO2-passivated silicon microwire array. Catal. Sci. Technol.2017, 7, 1488–1496.
Choi, S. K.; Piao, G. X.; Choi, W.; Park, H. Highly efficient hydrogen production using p-Si wire arrays and NiMoZn heterojunction photocathodes. Appl. Catal. B-Environ.2017, 217, 615–621.
Huang, Z. P.; Wang, C. F.; Pan, L.; Tian, F.; Zhang, X. X.; Zhang, C. Enhanced photoelectrochemical hydrogen production using silicon nanowires@MoS3. Nano Energy2013, 2, 1337–1346.
Basu, M.; Zhang, Z. W.; Chen, C. J.; Chen, P. T.; Yang, K. C.; Ma, C. G.; Lin, C. C.; Hu, S. F.; Liu, R. S. Heterostructure of Si and CoSe2: A promising photocathode based on a non-noble metal catalyst for photoelectrochemical hydrogen evolution. Angew. Chem., Int. Ed.2015, 54, 6211–6216.
Seger, B.; Pedersen, T.; Laursen, A. B.; Vesborg, P. C. K.; Hansen, O.; Chorkendorff, I. Using TiO2 as a conductive protective layer for photocathodic H2 evolution. J. Am. Chem. Soc.2013, 135, 1057–1064.
Seger, B.; Laursen, A. B.; Vesborg, P. C. K.; Pedersen, T.; Hansen, O.; Dahl, S.; Chorkendorff, I. Hydrogen production Nano Research using a molybdenum sulfide catalyst on a titanium-protected n plus p-silicon photocathode. Angew. Chem., Int. Ed.2012, 51, 9128–9131.
Bae, D.; Shayestehaminzadeh, S.; Thorsteinsson, E. B.; Pedersen, T.; Hansen, O.; Seger, B.; Vesborg, P. C. K.; Olafsson, S.; Chorkendorff, I. Protection of Si photocathode using TiO2 deposited by high power impulse magnetron sputtering for H2 evolution in alkaline media. Sol. Energy Mater. Sol. Cell2016, 144, 758–765.
Bao, X. Q.; Liu, L. F. Improved photo-stability of silicon nanobelt arrays by atomic layer deposition for efficient photocatalytic hydrogen evolution. J. Power Sources2014, 268, 677–682.
Tian, J. Q.; Liu, Q.; Asiri, A. M.; Sun, X. P. Self-supported nanoporous cobalt phosphide nanowire arrays: An efficient 3D hydrogen-evolving cathode over the wide range of pH 0–14. J. Am. Chem. Soc.2014, 136, 7587–7590.
Callejas, J. F.; Read, C. G.; Popczun, E. J.; McEnaney, J. M.; Schaak, R. E. Nanostructured Co2P electrocatalyst for the hydrogen evolution reaction and direct comparison with morphologically equivalent CoP. Chem. Mater.2015, 27, 3769–3774.
Choi, S. K.; Chae, W. S.; Song, B.; Cho, C. H.; Choi, J.; Han, D. S.; Choi, W.; Park, H. Photoelectrochemical hydrogen production on silicon microwire arrays overlaid with ultrathin titanium nitride. J. Mater. Chem. A2016, 4, 14008–14016.
Zhang, C. T.; Pu, Z. H.; Amiinu, I. S.; Zhao, Y. F.; Zhu, J. W.; Tang, Y. F.; Mu, S. C. Co2P quantum dot embedded N,P dual-doped carbon self-supported electrodes with flexible and binder-free properties for efficient hydrogen evolution reactions. Nanoscale2018, 10, 2902–2907.
Doan-Nguyen, V. V. T.; Zhang, S.; Trigg, E. B.; Agarwal, R.; Li, J.; Su, D.; Winey, K. I.; Murray, C. B. Synthesis and X-ray characterization of cobalt phosphide (Co2P) nanorods for the oxygen reduction reaction. ACS Nano2015, 9, 8108–8115.
Blanchard, P. E. R.; Grosvenor, A. P.; Cavell, R. G.; Mar, A. X-ray photoelectron and absorption spectroscopy of metal-rich phosphides M2P and M3P (M = Cr-Ni). Chem. Mater.2008, 20, 7081–7088.
Huang, Z. P.; Zhong, P.; Wang, C. F.; Zhang, X. X.; Zhang, C. Silicon nanowires/reduced graphene oxide composites for enhanced photoelectrochemical properties. ACS Appl. Mater. Interfaces2013, 5, 1961–1966.
Sim, U.; Moon, J.; An, J.; Kang, J. H.; Jerng, S. E.; Moon, J.; Cho, S. P.; Hong, B. H.; Nam, K. T. N-doped graphene quantum sheets on silicon nanowire photocathodes for hydrogen production. Energy Environ. Sci.2015, 8, 1329–1338.
Esposito, D. V.; Levin, I.; Moffat, T. P.; Talin, A. A. H2 evolution at Si-based metal-insulator-semiconductor photoelectrodes enhanced by inversion channel charge collection and H spillover. Nat. Mater.2013, 12, 562–568.
Hu, S.; Shaner, M. R.; Beardslee, J. A.; Lichterman, M.; Brunschwig, B. S.; Lewis, N. S. Amorphous TiO2 coatings stabilize Si, GaAs, and GaP photoanodes for efficient water oxidation. Science2014, 344, 1005–1009.
Erlebacher, J. An atomistic description of dealloying-porosity evolution, the critical potential, and rate-limiting behavior. J. Electrochem. Soc.2004, 151, C614–C626.
Acknowledgements
This work was funded by ERDF funds through the Portuguese Operational Programme for Competitiveness and Internationalization COMPETE 2020, and national funds through FCT–The Portuguese Foundation for Science and Technology, under the project “PTDC/ CTM-ENE/2349/2014” (Grant Agreement No. 016660). The work is also partially funded by the Portugal-China Bilateral Collaborative Programme (FCT/21102/28/12/2016/S). L. F. Liu acknowledges the financial support of the FCT Investigator Grant (IF/01595/2014) and Exploratory Grant (IF/01595/2014/CP1247/CT0001). L. Qiao acknowledges the financial support of the Ministry of Science and Technology of China (Grant Agreement No. 2016YFE0132400).
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Conformal and continuous deposition of bifunctional cobalt phosphide layers on p-silicon nanowire arrays for improved solar hydrogen evolution
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Thalluri, S.M., Borme, J., Yu, K. et al. Conformal and continuous deposition of bifunctional cobalt phosphide layers on p-silicon nanowire arrays for improved solar hydrogen evolution. Nano Res. 11, 4823–4835 (2018). https://doi.org/10.1007/s12274-018-2070-4
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DOI: https://doi.org/10.1007/s12274-018-2070-4