전이금속 디칼코제나이드 나노촉매를 이용한 태양광 흡수 광화학적 물분해 연구
Transition Metal Dichalcogenide Nanocatalyst for Solar-Driven Photoelectrochemical Water Splitting
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초록
태양광 흡수 물분해는 화석연료 대체 에너지원으로 떠오르는 수소에너지를 생산할 수 있는 가장유망한 방법이다. 현재 전이 금속 디칼코제나이드 (transition dichalcogenide, TMD)는 물분해촉매 특성이 뛰어난 물질로 많은 관심을 끌고 있다. 본 연구에서는 실리콘 (Si) 나노선 어레이전극 표면에 대표적 TMD 물질인 4-6족의 이황화 몰리브덴 (MoS2), 이셀렌화 몰리브덴(MoSe2), 이황화 텅스텐 (WS2), 이셀렌화 텅스텐 (WSe2) 나노시트 합성할 수 있는 방법을 개발하였다. Si나노선 전극을 금속 이온 용액으로 코팅하고, 황 또는 셀레늄의 화학 기상 증착법(chemical vapor deposition)을 이용하는 것이다. 이 방법으로 TMD 나노시트를 약 20 nm 두께로 균일하게 합성하였다. p형 Si-TMD 나노선 광전극으로 구성된 광화학전지는 태양광AM1.5G, 0.5 M H2SO4 전해질에서 개시 전위 0.2 V를 가지며 0 V (vs. RHE)에서20 mA cm-2 이상의 전류를 낼 수 있다. 수소 발생 양자효율은 90% 정도로 우수한 물분해 촉매특성을 확인하였다. MoS2 및 MoSe2는 3시간 동안 90% 이상의 우수한 광전류 안전성을 보여주었으나, WS2 및 WSe2는 상대적으로 적은 80%였다. MoS2, MoSe2는 Si 나노선 표면에 균일한 시트 형태로 씌워졌지만, WS2, WSe2는 조각 형태로 붙었다. 따라서 Si 표면을 잘 보호하지못하기 때문에 Si나노선이 더 잘 산화되어 안정성이 낮아지는 것으로 해석하였다. 본 연구결과는TMD의 수소 발생 촉매 특성을 이해하는 데 크게 기여할 것으로 예상한다.
Abstract
Photoelectrochemical water splitting has been considered as the most promising technology for generating hydrogen energy. Transition metal dichalcogenide (TMD) compounds have currently attracted tremendous attention due to their outstanding ability towards the catalytic water-splitting hydrogen evolution reaction (HER). Herein, we report the synthesis method of various transition metal dichalcogenide including MoS2, MoSe2, WS2, and WSe2 nanosheets as excellent catalysts for solar-driven photoelectrochemical (PEC) hydrogen evolution. Photocathodes were fabricated by growing the nanosheets directly onto Si nanowire (NW) arrays, with a thickness of 20 nm. The metal ion layers were formed by soaking the metal chloride ethanol solution and subsequent sulfurization or selenization produced the transition metal chalcogenide. They all exhibit excellent PEC performance in 0.5 M H2SO4; the photocurrent reaches to 20 mA cm-2 (at 0 V vs. RHE) and the onset potential is 0.2 V under AM1.5 condition. The quantum efficiency of hydrogen generation is avg. 90%. The stability of MoS2 and MoSe2 is 90% for 3h, which is higher than that (80%) of WS2 and WSe2. Detailed structure analysis using X-ray photoelectron spectroscopy for before/after HER reveals that the Si- WS2 and Si-WSe2 experience more oxidation of Si NWs than Si-MoS2 and Si-MoSe2. This can be explained by the less protection of Si NW surface by their flake shape morphology. The high catalytic activity of TMDs should be the main cause of this enhanced PEC performance, promising efficient water-splitting Si-based PEC cells.
참고문헌 (43)
- A. Fujishima, "Electrochemical Photolysis of Water at a Semiconductor Electrode", Nature, 238, pp.37~38 (1972)
- R. N. Dominey, "Improvement of Photoelectrochemical Hydrogen Generation by Surface Modification of p-Type Silicon Semiconductor Photocathodes", J. Am. Chem. Soc, 104, pp.467~482 (1982)
- O. Khaselev, "Monolithic Photovoltaic-Photoelectrochemical Device for Hydrogen Production via Water Splitting", Science, 280, pp.425~427 (1998)
- W. G. Walter, "Solar Water Splitting Cells", Chem. Rev, 110, pp.6446~6473 (2010)
- A. Paracchino, "Highly Active Oxide Photocathode for Photoelectrochemical Water Reduction", Nat. Mater, 10, pp.456~461 (2011)
- Y. Hou, "Bioinspired Molecular Co-Catalysts Bonded to a Silicon Photocathode for Solar Hydrogen Evolution", Nat. Mater, 10, pp.434~438 (2011)
- Y. W. Chen, "Atomic Layerdeposited Tunnel Oxide Stabilizes Silicon Photoanodes for Water Oxidation", Nat. Mater, 10, pp.539~544 (2011)
- S. Y. Reece, "Wireless Solar Water Splitting Using Silicon-Based Semiconductors and Earth-Abundant Catalysts", Science, 334, pp.645~648 (2011)
- M. J. Kenney, "High-Performance Silicon Photoanodes Passivated with Ultrathin Nickel Films for Water Oxidation", Science, 342, pp.836~840 (2013)
- K. Sun, "Enabling Silicon for Solar-Fuel Production", Chem. Rev, 114, pp.8662~8719 (2014)
- L. Ji, "A Silicon-Based Photocathode for Water Reduction with an Epitaxial SrTiO3 Protection Layer and a Nanostructured Catalyst", Nat. Nanotech, 10, pp.84~90 (2015)
- J. C. Hill, "An Electrodeposited Inhomogeneous Metal-Insulator-Semiconductor Junction for Efficient Photoelectrochemical Water Oxidation", Nat. Nanotech, 14, pp.1150~1155 (2015)
- Z. Huang, "Enhanced Photoelectrochemical Hydrogen Production Using Silicon Nanowires@MoS3", Nano Energy, 2, pp.1337~1346 (2013)
- J. Y. Jung, "Photoelectrochemical Water Splitting Employing a Tapered Silicon Nanohole Array", J. Mater. Chem. A, 2, pp.833~842 (2014)
- C. W. Roske, "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, 6, pp.1679~1683 (2015)
- M. Basu, "Heterostructure of Si and CoSe2: A Promising Photocathode Based on a Non-Noble Metal Catalyst for Photoelectrochemical Hydrogen Evolution", Angew. Chem. Int. Ed, 54, pp.6211~6216 (2015)
- C. Lv, "Silicon Nanowires Loaded with Iron Phosphide for Effective Solar-Driven Hydrogen Production", J. Mater. Chem. A, 3, pp.17669~17675 (2015)
- Q. Ding, "Designing Efficient Solar-Driven Hydrogen Evolution Photocathodes Using Semitransparent MoQxCly (Q = S, Se) Catalysts on Si Micropyramids", Adv. Mater, 27, pp.6511~6518 (2015)
- H. Zhang, "A p-Si", NiCoSex Core, Energy Environ. Sci, pp.2016, 9[DOI]
- D. Liu, "Silicon Nanostructures for Solar-Driven Catalytic Applications", Nano Today, 17, pp.96~116 (2017)
- C. J. Chen, "Silicon Microwire Arrays Decorated with Amorphous Heterometal-Doped Molybdenum Sulfide for Water Photoelectrolysis", Nano Energy, 32, pp.422~432 (2017)
- W. Vijselaar, "Efficient and Stable Silicon Microwire Photocathodes with a Nickel Silicide Interlayer for Operation in Strongly Alkaline Solutions", ACS Energy Lett, 3, pp.1086~1092 (2018)
- S. Lee, "Orthorhombic NiSe2 Nanocrystals on Si Nanowires for Efficient Photoelectrochemical Water Splitting", ACS Appl. Mater. Interfaces, 10, pp.33196~33204 (2018)
- D. Hu, "One-step Chemical Vapor Deposition of MoS2Nanosheets on SiNWs as Photocathodes for Efficient and Stable Solar-Driven Hydrogen Production", Nanoscale, 10, pp.3518~3525 (2018)
- X. Sun, "Enhancing the Performance of Si-Based Photocathodes for Solar Hydrogen Production in Alkaline Solution by Facilely Intercalating a Sandwich N-Doped Carbon Nanolayer to the Interface of Si and TiO2", ACS Appl. Mater. Interfaces, 11, pp.19132~19140 (2019)
- P. D. Tran, "Novel Assembly of an MoS2 Electrocatalyst onto a Silicon Nanowire Array Electrode to Construct a Photocathode Composed of Elements Abundant on the Earth for Hydrogen Generation", Chem. Eur. J, 18, pp.13994~13999 (2012)
- Q. Ding, "Novel Assembly of an MoS2 Electrocatalyst onto a Silicon Nanowire Array Electrode to Construct a Photocathode Composed of Elements Abundant on the Earth for Hydrogen Generation", J. Am. Chem. Soc, 136, pp.8504~8507 (2014)
- L. Zhang, "Novel Assembly of an MoS2 Electrocatalyst onto a Silicon Nanowire Array Electrode to Construct a Photocathode Composed of Elements Abundant on the Earth for Hydrogen Generation", Nano Res, 8, pp.281~287 (2015)
- K. C. Kwon, "Wafer-scale Transferable Molybdenum Disulfide Thin-film Catalysts for Photoelectrochemical Hydrogen Production", Energy Environ. Sci, 9, pp.2240~2248 (2016)
- S. Oh, "Atomic Layer Deposited Molybdenum Disulfide on Si Photocathodes for Highly Efficient Photoelectrochemical Water Reduction Reaction", J. Mater. Chem. A, 5, pp.3304~3310 (2017)
- L. A. King, "Highly Stable Molybdenum Disulfide Protected Silicon Photocathodes for Photoelectrochemical Water Splitting", ACS Appl. Mater. Interfaces, 9, pp.36792~36798 (2017)
- R. Fan, "Efficient and Stable Silicon Photocathodes Coated with Vertically Standing Nano-MoS2 Films for Solar Hydrogen Production", ACS Appl. Mater. Interfaces, 9, pp.6123~6129 (2017)
- Yi. Hou, "Efficient Photoelectrochemical Hydrogen Production Over p-Si Nanowire Arrays Coupled with Molybdenume-Sulfur Clusters", J. Hydrog. Energy, 42, pp.2832~2838 (2017)
- D. M. Andoshe, "Directly Assembled 3D Molybdenum Disulfide on Silicon Wafer for Efficient Photoelectrochemical Water Reduction", Adv. Sustainable Syst, 2, pp.1700142~ (2018)
- Q. Zhou, "Ultrathin MoS2-coated Ag@Si Nanosphere Arrays as an Efficient and Stable Photocathode for Solar-driven Hydrogen Production", Nanotechnology, 29, pp.105402~ (2018)
- J. Joe, "Mixed-Phase (2H and 1T) MoS2 Catalyst for a Highly Efficient and Stable Si Photocathode", Catalysts, 8, pp.580~ (2018)
- M. Alqahtani, "Heteroepitaxy of GaP on Silicon for Efficient and Costeffective Photoelectrochemical Water Splitting", J. Mater. Chem. A, 7, pp.8550~8558 (2019)
- R. Fan, "Efficient n+p-Si Photocathodes for Solar H2 Production Catalyzed by Co-W-S and Stabilized by Ti Buffer Layer", Appl. Catal. B, 237, pp.158~165 (2018)
- G. Huang, "Integrated MoSe2 with n+p-Si Photocathodes for Solar Water Splitting with High Efficiency and Stability", Appl. Phys. Lett, 112, pp.013902~ (2018)
- A. Hasani, "Fabrication of a WS2", p-Si Heterostructure Photocathode Using Direct Hybrid Thermolysis, 2019, pp.11, 29910~29916
- I. H. Kwak, "Intercalated Complexes of 1T’-MoS2 Nanosheets with Alkylated Phenylenediamines as Excellent Catalysts for Electrochemical Hydrogen Evolution", J. Mater. Chem. A, 7, pp.2334~2343 (2019)
- J. He, "Stacking Effects on the Electronic and Optical Properties of Bilayer Transition Metal Dichalcogenides MoS2, MoSe2, WS2, and WSe2", Phys. Rev. B, 89, pp.075409~ (2014)
- F. Zeng, "Electronic Structures and Elastic Properties of Monolayer and Bilayer Transition Metal Dichalcogenides MX2 (M = Mo, W; X = O, S, Se, Te): A Comparative First-Principles Study", Chin. Phys. B, 24, pp.097103~ (2015)