Issue

Vol. 13 (2021)

Direct Synthesis of Molybdenum Phosphide Nanorods on Silicon Using Graphene at the Heterointerface for Efficient Photoelectrochemical Water Reduction

https://doi.org/10.1007/s40820-021-00605-7
Sang Eon Jun
Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea
Seokhoon Choi
Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea
Shinyoung Choi
Department of Chemical Engineering, Pohang University of Science and Technology, Pohang 37673, Republic of Korea
Tae Hyung Lee
Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea
Changyeon Kim
Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea
Jin Wook Yang
Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea
Woon‑Oh Choe
Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea
In‑Hyuk Im
Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea
Cheol‑Joo Kim
Department of Chemical Engineering, Pohang University of Science and Technology, Pohang 37673, Republic of Korea
Ho Won Jang
Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea

Corresponding Author: Ho Won Jang

kimcj@postech.ac.kr

Nano-Micro Letters, Vol. 13 (2021), Article Number: 81

Abstract

Transition metal phosphides (TMPs) and transition metal dichalcogenides (TMDs) have been widely investigated as photoelectrochemical (PEC) catalysts for hydrogen evolution reaction (HER). Using high-temperature processes to get crystallized compounds with large-area uniformity, it is still challenging to directly synthesize these catalysts on silicon photocathodes due to chemical incompatibility at the heterointerface. Here, a graphene interlayer is applied between p-Si and MoP nanorods to enable fully engineered interfaces without forming a metallic secondary compound that absorbs a parasitic light and provides an inefficient electron path for hydrogen evolution. Furthermore, the graphene facilitates the photogenerated electrons to rapidly transfer by creating Mo-O-C covalent bondings and energetically favorable band bending. With a bridging role of graphene, numerous active sites and anti-reflectance of MoP nanorods lead to significantly improved PEC-HER performance with a high photocurrent density of 21.8 mA cm−2 at 0 V versus RHE and high stability. Besides, low dependence on pH and temperature is observed with MoP nanorods incorporated photocathodes, which is desirable for practical use as a part of PEC cells. These results indicate that the direct synthesis of TMPs and TMDs enabled by graphene interlayer is a new promising way to fabricate Si-based photocathodes with high-quality interfaces and superior HER performance.


Highlights:


1 MoP nanorod-array catalysts were directly synthesized on graphene passivated silicon photocathodes without secondary phase.
2 Mo-O-C covalent bondings and energy band bending at heterointerfaces facilitate the electron transfer to the reaction sites.
3 Numerous catalytic sites and drastically enhanced anti-reflectance of MoP nanorods contribute to the high solar energy conversion efficiency.

Keywords

Photoelectrochemical water splitting Silicon Molybdenum phosphide Hydrogen evolution Graphene
Jun, Sang Eon, Seokhoon Choi, Shinyoung Choi, Tae Hyung Lee, Changyeon Kim, Jin Wook Yang, Woon‑Oh Choe, In‑Hyuk Im, Cheol‑Joo Kim, and Ho Won Jang. 2021. “Direct Synthesis of Molybdenum Phosphide Nanorods on Silicon Using Graphene at the Heterointerface for Efficient Photoelectrochemical Water Reduction”. Nano-Micro Letters 13 (March):81. https://doi.org/10.1007/s40820-021-00605-7.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. W. Lubitz, W. Tumas, Hydrogen: an overview. Chem. Rev. 107, 3900 (2007). https://doi.org/10.1021/cr050200z
  2. N. Armaroli, V. Balzani, Solar electricity and solar fuels: status and perspectives in the context of the energy transition. Chem. Eur. J. 22, 32–57 (2016). https://doi.org/10.1002/chem.201503580
  3. X. Li, L. Zhao, J. Yu, X. Liu, X. Zhang et al., Water splitting: from electrode to green energy system. Nano-Micro Lett. 12, 131 (2020). https://doi.org/10.1007/s40820-020-00469-3
  4. I. Roger, M.A. Shipman, M.D. Symes, Earth-abundant catalysts for electrochemical and photoelectrochemical water splitting. Nat. Rev. Chem. 1, 1–13 (2017). https://doi.org/10.1038/s41570-016-0003
  5. S.A. Lee, T.H. Lee, C. Kim, M.G. Lee, M.-J. Choi et al., Tailored NiOx/Ni cocatalysts on silicon for highly efficient water splitting photoanodes via pulsed electrodeposition. ACS Catal. 8, 7261–7269 (2018). https://doi.org/10.1021/acscatal.8b01999
  6. R.J. Britto, J.D. Benck, J.L. Young, C. Hahn, T.G. Deutsch et al., Molybdenum disulfide as a protection layer and catalyst for gallium indium phosphide solar water splitting photocathodes. J. Phys. Chem. Lett. 7, 2044–2049 (2016). https://doi.org/10.1021/acs.jpclett.6b00563
  7. D. Kang, J.L. Young, H. Lim, W.E. Klein, H. Chen et al., Printed assemblies of GaAs photoelectrodes with decoupled optical and reactive interfaces for unassisted solar water splitting. Nat. Energy 2, 17043 (2017). https://doi.org/10.1038/nenergy.2017.43
  8. O. Gunawan, L. Sekaric, A. Majumdar, M. Rooks, J. Appenzeller et al., Measurement of carrier mobility in silicon nanowires. Nano Lett. 8, 1566–1571 (2008). https://doi.org/10.1021/nl072646w
  9. C. Strümpel, M. McCann, G. Beaucarne, V. Arkhipov, A. Slaoui et al., Modifying the solar spectrum to enhance silicon solar cell efficiency-An overview of available materials. Sol. Energy Mater. Sol. Cells 91, 238–249 (2007). https://doi.org/10.1016/j.solmat.2006.09.003
  10. M.G. Walter, E.L. Warren, J.R. McKone, S.W. Boettcher, Q. Mi et al., Solar water splitting cells. Chem. Rev. 110, 6446–6473 (2010). https://doi.org/10.1021/cr1002326
  11. S. Chen, L.-W. Wang, Thermodynamic oxidation and reduction potentials of photocatalytic semiconductors in aqueous solution. Chem. Mater. 24, 3659–3666 (2012). https://doi.org/10.1021/cm302533s
  12. C.-J. Chen, K.-C. Yang, C.-W. Liu, Y.-R. Lu, C.-L. Dong et al., Silicon microwire arrays decorated with amorphous heterometal-doped molybdenum sulfide for water photoelectrolysis. Nano Energy 32, 422–432 (2017). https://doi.org/10.1016/j.nanoen.2016.12.045
  13. G. Li, D. Zhang, Q. Qiao, Y. Yu, D. Peterson et al., All the catalytic active sites of MoS2 for hydrogen evolution. J. Am. Chem. Soc. 138, 16632–16638 (2016). https://doi.org/10.1021/jacs.6b05940
  14. S. Zheng, L. Zheng, Z. Zhu, J. Chen, J. Kang et al., MoS2 nanosheet arrays rooted on hollow rGO spheres as bifunctional hydrogen evolution catalyst and supercapacitor electrode. Nano-Micro Lett. 10, 62 (2018). https://doi.org/10.1007/s40820-018-0215-3
  15. M.-L. Tsai, S.-H. Su, J.-K. Chang, D.-S. Tsai, C.-H. Chen et al., Monolayer MoS2 heterojunction solar cells. ACS Nano 8, 8317–8322 (2014). https://doi.org/10.1021/nn502776h
  16. T. Chu, H. Ilatikhameneh, G. Klimeck, R. Rahman, Z. Chen, Electrically tunable bandgaps in bilayer MoS2. Nano Lett. 15, 8000–8007 (2015). https://doi.org/10.1021/acs.nanolett.5b03218
  17. J. Lin, Y. Yan, C. Li, X. Si, H. Wang et al., Bifunctional electrocatalysts based on Mo-doped NiCoP nanosheet arrays for overall water splitting. Nano-Micro Lett. 11, 55 (2019). https://doi.org/10.1007/s40820-019-0289-6
  18. K.C. Kwon, S. Choi, K. Hong, C.W. Moon, Y.-S. Shim et al., Wafer-scale transferable molybdenum disulfide thin-film catalysts for photoelectrochemical hydrogen production. Energy Environ. Sci. 9, 2240–2248 (2016). https://doi.org/10.1039/C6EE00144K
  19. K.C. Kwon, S. Choi, K. Hong, D.M. Andoshe, J.M. Suh et al., Tungsten disulfide thin film/p-type Si heterojunction photocathode for efficient photochemical hydrogen production. MRS Commun. 7, 272 (2017). https://doi.org/10.1557/mrc.2017.37
  20. K.C. Kwon, S. Choi, J. Lee, K. Hong, W. Sohn et al., 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. J. Mater. Chem. A 5, 15534–15542 (2017). https://doi.org/10.1039/C7TA03845C
  21. P. Gnanasekar, D. Periyanagounder, P. Varadhan, J.-H. He, J. Kulandaivel, Highly efficient and stable photoelectrochemical hydrogen evolution with 2D-NbS2/Si nanowire heterojunction. ACS Appl. Mater. Interfaces 11, 44179–44185 (2019). https://doi.org/10.1021/acsami.9b14713
  22. S. Seo, S. Kim, H. Choi, J. Lee, H. Yoon et al., Direct in situ growth of centimeter-scale multi-heterojunction MoS2/WS2/WSe2 thin-film catalyst for photo-electrochemical hydrogen evolution. Adv. Sci. 6, 1900301 (2019). https://doi.org/10.1002/advs.201900301
  23. Q. Ding, J. Zhai, M. Cabán-Acevedo, M.J. Shearer, L. Li et al., Designing efficient solar-driven hydrogen evolution photocathodes using semitransparent MoQxCly (Q= S, Se) catalysts on Si Micropyramids. Adv. Mater. 27, 6511–6518 (2015). https://doi.org/10.1002/adma.201501884
  24. T.R. Hellstern, J.D. Benck, J. Kibsgaard, C. Hahn, T.F. Jaramillo, Engineering cobalt phosphide (CoP) thin film catalysts for enhanced hydrogen evolution activity on silicon photocathodes. Adv. Energy Mater. 6, 1501758 (2016). https://doi.org/10.1002/aenm.201501758
  25. J.D. Benck, S.C. Lee, K.D. Fong, J. Kibsgaard, R. Sinclair et al., Designing active and stable silicon photocathodes for solar hydrogen production using molybdenum sulfide nanomaterials. Adv. Energy Mater. 4, 1400739 (2014). https://doi.org/10.1002/aenm.201400739
  26. A. Hasani, Q. Van Le, M. Tekalgne, M.-J. Choi, T.H. Lee et al., Direct synthesis of two-dimensional MoS2 on p-type Si and application to solar hydrogen production. NPG Asia Mater. 11, 1–9 (2019). https://doi.org/10.1038/s41427-019-0145-7
  27. R. Liu, D. Williams, W. Lynch, A study of the leakage mechanisms of silicided n+/p junctions. J. Appl. Phys. 63, 1990–1999 (1988). https://doi.org/10.1063/1.341099
  28. P. Sharma, T. Kaur, O.P. Pandey, In situ single-step reduction and silicidation of MoO3 to form MoSi2. J. Am. Ceram. Soc. 102, 1522–1534 (2019). https://doi.org/10.1111/jace.15994
  29. K.F. Mak, J. Shan, T.F. Heinz, Seeing many-body effects in single-and few-layer graphene: observation of two-dimensional saddle-point excitons. Phys. Rev. Lett. 106, 046401 (2011). https://doi.org/10.1103/PhysRevLett.106.046401
  30. E. Samuel, B. Joshi, M.-W. Kim, M.T. Swihart, S.S. Yoon, Morphology engineering of photoelectrodes for efficient photoelectrochemical water splitting. Nano Energy (2020). https://doi.org/10.1016/j.nanoen.2020.104648
  31. J. Li, W. Xu, J. Luo, D. Zhou, D. Zhang et al., Synthesis of 3D hexagram-like cobalt-manganese sulfides nanosheets grown on nickel foam: a bifunctional electrocatalyst for overall water splitting. Nano-Micro Lett. 10, 6 (2018). https://doi.org/10.1007/s40820-017-0160-6
  32. J. Li, H.-X. Liu, W. Gou, M. Zhang, Z. Xia et al., Ethylene-glycol ligand environment facilitates highly efficient hydrogen evolution of Pt/CoP through proton concentration and hydrogen spillover. Energy Environ. Sci. 12, 2298–2304 (2019). https://doi.org/10.1039/C9EE00752K
  33. P. Xiao, M.A. Sk, L. Thia, X. Ge, R.J. Lim et al., Molybdenum phosphide as an efficient electrocatalyst for the hydrogen evolution reaction. Energy Environ. Sci. 7, 2624–2629 (2014). https://doi.org/10.1039/C4EE00957F
  34. D. Zhan, J. Yan, L. Lai, Z. Ni, L. Liu et al., Engineering the electronic structure of graphene. Adv. Mater. 24, 4055–4069 (2012). https://doi.org/10.1002/adma.201200011
  35. M.G. Lee, W. Sohn, C.W. Moon, H. Park, S. Lee et al., Conformally coated BiVO4 nanodots on porosity-controlled WO3 nanorods as highly efficient type II heterojunction photoanodes for water oxidation. Nano Energy 28, 250–260 (2016). https://doi.org/10.1016/j.nanoen.2016.08.046
  36. D.M. Andoshe, S. Choi, Y.-S. Shim, S.H. Lee, Y. Kim et al., A wafer-scale antireflective protection layer of solution-processed TiO2 nanorods for high performance silicon-based water splitting photocathodes. J. Mater. Chem. A 4, 9477–9485 (2016). https://doi.org/10.1039/C6TA02987F
  37. S. Deng, K. Zhang, D. Xie, Y. Zhang, Y. Zhang et al., High-index-faceted Ni3S2 branch arrays as bifunctional electrocatalysts for efficient water splitting. Nano-Micro Lett. 11, 12 (2019). https://doi.org/10.1007/s40820-019-0242-8
  38. R. Ye, P. del Angel-Vicente, Y. Liu, M.J. Arellano-Jimenez, Z. Peng et al., High-performance hydrogen evolution from MoS2(1–x)Px solid solution. Adv. Mater. 28, 1427–1432 (2016). https://doi.org/10.1002/adma.201504866
  39. Z. Xing, Q. Liu, A.M. Asiri, X. Sun, Closely interconnected network of molybdenum phosphide nanoparticles: a highly efficient electrocatalyst for generating hydrogen from water. Adv. Mater. 26, 5702–5707 (2014). https://doi.org/10.1002/adma.201401692
  40. M.L. Brongersma, Y. Cui, S. Fan, Light management for photovoltaics using high-index nanostructures. Nat. Mater. 13, 451–460 (2014). https://doi.org/10.1038/nmat3921
  41. J.-Q. Xi, M.F. Schubert, J.K. Kim, E.F. Schubert, M. Chen et al., Optical thin-film materials with low refractive index for broadband elimination of Fresnel reflection. Nat. Photon. 1, 176–179 (2007). https://doi.org/10.1038/nphoton.2007.26
  42. U. Sim, T.-Y. Yang, J. Moon, J. An, J. Hwang et al., N-doped monolayer graphene catalyst on silicon photocathode for hydrogen production. Energy Environ. Sci. 6, 3658–3664 (2013). https://doi.org/10.1039/c3ee42106f
  43. L.G. Cançado, A. Jorio, E.M. Ferreira, F. Stavale, C.A. Achete et al., Quantifying defects in graphene via Raman spectroscopy at different excitation energies. Nano Lett. 11, 3190–3196 (2011). https://doi.org/10.1021/nl201432g
  44. A. Eckmann, A. Felten, I. Verzhbitskiy, R. Davey, C. Casiraghi, Raman study on defective graphene: Effect of the excitation energy, type, and amount of defects. Phys. Rev. B 88, 035426 (2013). https://doi.org/10.1103/PhysRevB.88.035426
  45. Y. Zhang, Z. Li, P. Kim, L. Zhang, C. Zhou, Anisotropic hydrogen etching of chemical vapor deposited graphene. ACS Nano 6, 126–132 (2012). https://doi.org/10.1021/nn202996r
  46. V.K. Singh, S. Kumar, S.K. Pandey, S. Srivastava, M. Mishra et al., Fabrication of sensitive bioelectrode based on atomically thin CVD grown graphene for cancer biomarker detection. Biosens. Bioelectron. 105, 173–181 (2018). https://doi.org/10.1016/j.bios.2018.01.014
  47. S. Bai, C. Chen, R. Luo, A. Chen, D. Li, Synthesis of MoO3/reduced graphene oxide hybrids and mechanism of enhancing H2S sensing performances. Sensors Actuat. B Chem. 216, 113–120 (2015). https://doi.org/10.1016/j.snb.2015.04.036
  48. A. Chithambararaj, N. Sanjini, A.C. Bose, S. Velmathi, Flower-like hierarchical h-MoO3: new findings of efficient visible light driven nano photocatalyst for methylene blue degradation. Catal. Sci. Technol. 3, 1405–1414 (2013). https://doi.org/10.1039/C3CY20764A
  49. D. He, Z. Peng, W. Gong, Y. Luo, P. Zhao et al., Mechanism of a green graphene oxide reduction with reusable potassium carbonate. RSC Adv. 5, 11966–11972 (2015). https://doi.org/10.1039/C4RA14511A
  50. S. Verma, R.K. Dutta, A facile method of synthesizing ammonia modified graphene oxide for efficient removal of uranyl ions from aqueous medium. RSC Adv. 5, 77192–77203 (2015). https://doi.org/10.1039/C5RA10555B
  51. H. Zhang, D. Hines, D.L. Akins, Synthesis of a nanocomposite composed of reduced graphene oxide and gold nanoparticles. Dalton Trans. 43, 2670–2675 (2014). https://doi.org/10.1039/C3DT52573B
  52. M. Dhanasankar, K. Purushothaman, G. Muralidharan, Effect of temperature of annealing on optical, structural and electrochromic properties of sol-gel dip coated molybdenum oxide films. Appl. Surf. Sci. 257, 2074–2079 (2011). https://doi.org/10.1016/j.apsusc.2010.09.052
  53. A. Klinbumrung, T. Thongtem, S. Thongtem, Characterization of orthorhombic α-MoO3 microplates produced by a microwave plasma process. J. Nanomater. 2012, 5 (2012). https://doi.org/10.1155/2012/930763
  54. J.E. Johns, M.C. Hersam, Atomic covalent functionalization of graphene. Acc. Chem. Res. 46, 77–86 (2013). https://doi.org/10.1021/ar300143e
  55. C.M. Proctor, T.-Q. Nguyen, Effect of leakage current and shunt resistance on the light intensity dependence of organic solar cells. Appl. Phys. Lett. 106, 083301 (2015). https://doi.org/10.1063/1.4913589
  56. Q. Ding, F. Meng, C.R. English, M. Cabán-Acevedo, M.J. Shearer et al., Efficient photoelectrochemical hydrogen generation using heterostructures of Si and chemically exfoliated metallic MoS2. J. Am. Chem. Soc. 136, 8504–8507 (2014). https://doi.org/10.1021/ja5025673
  57. S. Haussener, S. Hu, C. Xiang, A.Z. Weber, N.S. Lewis, Simulations of the irradiation and temperature dependence of the efficiency of tandem photoelectrochemical water-splitting systems. Energy Environ. Sci. 6, 3605–3618 (2013). https://doi.org/10.1039/C3EE41302K
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY MATERIAL
Statistic
Read Counter : 8382 Download : 6299

Most read articles by the same author(s)