T. R. Cook, D. K. Dogutan, S. Y. Reece, Y. Surendranath, T. S. Teets et al., Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds, Chem. Rev, vol.110, pp.6474-6502, 2010.

N. S. Lewis and D. G. Nocera, Powering the Planet: Chemical Challenges in Solar Energy Utilization, Proc. Natl. Acad. Sci, vol.103, pp.15729-15735, 2006.

M. G. Walter, E. L. Warren, J. R. Mckone, S. W. Boettcher, Q. Mi et al., Solar Water Splitting Cells, Chem. Rev, vol.110, pp.6446-6473, 2010.

K. Sun, S. Shen, Y. Liang, P. E. Burrows, S. S. Mao et al., Enabling Silicon for Solar-Fuel Production, Chem. Rev, vol.114, pp.8662-8719, 2014.

T. Yao, X. An, H. Han, J. Q. Chen, and C. Li, Photoelectrocatalytic Materials for Solar Water Splitting, Adv. Energy Mater, vol.8, p.1800210, 2018.

K. Sivula and R. Van-de-krol, Semiconducting Materials for Photoelectrochemical Energy Conversion, Nat. Rev. Mater, vol.1, pp.1-16, 2016.

C. G. Morales-guio and X. Hu, Amorphous Molybdenum Sulfides as Hydrogen Evolution Catalysts, Acc. Chem. Res, vol.47, pp.2671-2681, 2014.

B. Seger, A. B. Laursen, P. C. Vesborg, T. Pedersen, O. Hansen et al., Hydrogen Production Using a Molybdenum Sulfide Catalyst on a Titanium-Protected n + p-Silicon Photocathode, Angew. Chem. Int. Ed, vol.51, pp.9128-9131, 2012.

A. B. Laursen, T. Pedersen, P. Malacrida, B. Seger, O. Hansen et al., MoS 2 : An Integrated Protective and Active Layer on n(+)p-Si for Solar H 2 Evolution, Phys. Chem. Chem. Phys, vol.15, 2013.

P. D. Tran, S. S. Pramana, V. S. Kale, M. Nguyen, S. Y. Chiam et al., Novel Assembly of an MoS 2 Electrocatalyst onto a Silicon Nanowire Array Electrode to Construct a Photocathode Composed of Elements Abundant on the Earth for Hydrogen Generation, Chem. Eur. J, vol.18, pp.13994-13999, 2012.

Q. Ding, F. Meng, C. R. English, M. Caban-acevedo, M. J. Shearer et al., Efficient Photoelectrochemical Hydrogen Generation Using Heterostructures of Si and Chemically Exfoliated Metallic MoS 2, J. Am. Chem. Soc, vol.136, pp.8504-8507, 2014.

Q. Ding, J. Zhai, M. Caban-acevedo, M. J. Shearer, L. Li et al., Designing Efficient Solar-Driven Hydrogen Evolution Photocathodes Using Semitransparent MoQ x Cl y (Q = S, Se) Catalysts on Si Micropyramids, Adv. Mater, vol.27, pp.6511-6518, 2015.

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, 2014.

L. A. King, T. R. Hellstern, J. Park, R. Sinclair, and T. F. Jaramillo, Highly Stable Molybdenum Disulfide Protected Silicon Photocathodes for Photoelectrochemical Water Splitting, ACS Appl. Mater. Interf, vol.9, pp.36792-36798, 2017.

J. Kibsgaard, T. F. Jaramillo, and F. Besenbacher, Building an Appropriate Active-Site Motif into a Hydrogen-Evolution Catalyst with Thiomolybdate, Nature Chem, vol.6, pp.248-253, 2014.

T. R. Hellstern, J. Kibsgaard, C. Tsai, D. W. Palm, L. A. King et al., Investigating Catalyst-Support Interactions to Improve the Hydrogen Evolution Reaction Activity of Thiomolybdate, ACS Catal, vol.7, pp.7126-7130, 2017.

Y. Hou, B. L. Abrams, P. C. Vesborg, M. E. Björketun, K. Herbst et al., Bioinspired Molecular Co-Catalysts Bonded to a Silicon Photocathode for Solar Hydrogen Evolution, Nature Mater, vol.10, pp.434-438, 2011.

B. Seger, K. Herbst, T. Pedersen, B. Abrams, P. C. Vesborg et al., Mo 3 S 4 Clusters as an Effective H 2 Evolution Catalyst on Protected Si Photocathodes, J. Electrochem. Soc, vol.161, pp.722-724, 2014.

R. Dubois and M. , Catalytic Applications of Transition-Metal Complexes with Sulfide Ligands, Chem. Rev, vol.89, pp.1-9, 1989.

J. Launay, High Reduction Stages of [H 2 W 12 O 40 ] 6-Derivatives of HW 12 O 40 7-and General Discussion, J. Inorg. Nucl. Chem, vol.38, pp.807-816, 1976.

M. Sadakane and E. Steckhan, Electrochemical Properties of Polyoxometalates as Electrocatalysts, Chem. Rev, vol.98, pp.219-237, 1998.

T. Ueda, Electrochemistry of Polyoxometalates: From Fundamental Aspects to Applications, vol.5, pp.823-838, 2018.

H. Wang, S. Hamanaka, Y. Nishimoto, S. Irle, T. Yokoyama et al., In Operando X-Ray Absorption Fine Structure Studies of Polyoxometalate Molecular Cluster Batteries: Polyoxometalates as Electron Sponges, J. Am. Chem. Soc, vol.134, pp.4918-4924, 2012.

M. N. Sokolov, I. V. Kalinina, E. V. Peresypkina, E. Cadot, S. V. Tkachev et al., Incorporation of Molybdenum Sulfide Cluster Units into a Dawson-Like Polyoxometalate Structure To Give Hybrid Polythiooxometalates, Angew. Chem. Int. Ed, vol.47, pp.1465-1468, 2008.

E. Cadot, M. N. Sokolov, V. P. Fedin, C. Simonnet-jégat, S. Floquet et al., Building Block Strategy to Access SulfurFunctionalized Polyoxometalate Based Systems using {Mo 2 S 2 O 2 } and {Mo 3 S 4 } as Constitutional Units, Linkers or Templates, Chem. Soc. Rev, vol.41, pp.7335-7353, 2012.

D. Fu, B. Fabre, G. Loget, C. Meriadec, S. Ababou-girard et al., PolyoxothiometalateDerivatized Silicon Photocathodes for Sunlight-Driven HER, ACS Omega, vol.3, pp.13837-13849, 2018.

X. Bao, D. Y. Petrovykh, P. Alpuim, D. G. Stroppa, N. Guldris et al., Amorphous OxygenRich Molybdenum Oxysulfide Decorated p-Type Silicon Microwire Arrays for Efficient Photoelectrochemical Water Reduction, Nano Energy, vol.16, pp.130-142, 2015.

T. Truong, C. Mériadec, B. Fabre, J. Bergamini, O. De-sagazan et al., Spontaneous Decoration of Silicon Surfaces with MoO x Nanoparticles for the Sunlight-Assisted Hydrogen Evolution Reaction, vol.9, pp.1799-1804, 2017.

R. Contant and A. Teze, A New Crown Heteropolyanion

, Li 5 H 7 P 8 W 48 O 184 .92H 2 O: Synthesis, Structure, and Properties, vol.24, pp.4610-4614, 1985.

M. Haouas, M. Diab, M. A. Moussawi, E. Cadot, S. Floquet et al., Investigation of the Protonation State of the Macrocyclic {H n P 8 W 48 O 184 } Anion by Modeling 183 W NMR Chemical Shifts, New J. Chem, vol.41, pp.6112-6119, 2017.

T. Boyd, S. G. Mitchell, D. Gabb, D. Long, Y. Song et al., POMzites: A Family of Zeolitic Polyoxometalate Frameworks from a Minimal Building Block Library, J. Am. Chem. Soc, vol.139, pp.5930-5938, 2017.

B. S. Bassil, M. Ibrahim, S. S. Mal, A. Suchopar, R. N. Biboum et al.,

?. , Inorg. Chem, vol.49, pp.4949-4959, 2010.

M. Zimmermann, N. Belai, R. J. Butcher, M. T. Pope, E. V. Chubarova et al., New Lanthanide-Containing Polytungstates Derived from the Cyclic P 8 W 48 Anion: {Ln 4 (H 2 O) 28, Inorg. Chem, vol.46, pp.1737-1740, 2007.

F. L. Sousa, H. Bögge, A. Merca, P. Gouzerh, R. Thouvenot et al., Vectorial Growth/Regulations in a {P 8 W 48 }-Type Polyoxotungstate Compartment: Trapped Unusual Molybdenum Oxide Acts as a Handle, Chem. Commun, pp.7491-7493, 2009.

V. S. Korenev, S. Floquet, J. Marrot, M. Haouas, I. Mbomekallé et al., Oxothiomolybdenum Derivatives of the Superlacunary Crown Heteropolyanion {P 8 W 48 }: Structure of, Inorg. Chem, vol.51, issue.2, pp.2349-2358, 2012.

B. Keita, Y. W. Lu, L. Nadjo, and R. Contant, Salient Electrochemical and Electrocatalytic Behaviour of the Crown Heteropolyanion K 28 Li 5 H 7 P 8 W 48 O 184 ?92H 2 O, Electrochem. Commun, vol.2, pp.720-726, 2000.

J. Kristensen, J. D. Zhang, I. Chorkendorff, J. Ulstrup, and B. L. Ooi,

, Dalton Trans, pp.3985-3990, 2006.

S. A. Spanninga, D. C. Martin, and Z. Chen, X-Ray Photoelectron Spectroscopy Study of Counterion Incorporation in Poly(3,4-Ethylenedioxythiophene) (PEDOT). 2: Polyanion Effect, Toluenesulfonate, and Small Anions, J. Phys. Chem. C, vol.114, pp.14992-14997, 2010.

S. A. Spanninga, D. C. Martin, Z. Chen, and . X-ray, Photoelectron Spectroscopy Study of Counterion Incorporation in Poly(3,4-Ethylenedioxythiophene), J. Phys. Chem. C, vol.113, pp.5585-5592, 2009.

S. K. Jönsson, M. P. Jong, L. Groenendaal, W. R. Salaneck, and M. Fahlman, Phenyl-Capped EDOT Trimer: Its Chemical and Electronic Structure and Its Interface with Aluminum, J. Phys. Chem. B, vol.107, pp.10793-10800, 2003.

M. A. Khan, S. P. Armes, C. Perruchot, H. Ouamara, M. M. Chehimi et al., Surface Characterization of Poly(3,4-Ethylenedioxythiophene)-Coated Latexes by X-Ray Photoelectron Spectroscopy, Langmuir, vol.16, pp.4171-4179, 2000.

J. Baltrusaitis, B. Mendoza-sanchez, V. Fernandez, R. Veenstra, N. Dukstiene et al., Generalized Molybdenum Oxide Surface Chemical State XPS Determination via Informed Amorphous Sample Model, Appl. Surf. Sci, vol.326, pp.151-161, 2015.
URL : https://hal.archives-ouvertes.fr/hal-01725863

J. P. Bruce, D. R. Oliver, N. S. Lewis, and M. S. Freund, Electrical Characteristics of the Junction between PEDOT:PSS and ThiopheneFunctionalized Silicon Microwires, ACS Appl. Mater. Interfaces, vol.7, pp.27160-27166, 2015.

D. Merki, S. Fierro, H. Vrubel, and X. Hu, Amorphous Molybdenum Sulfide Films as Catalysts for Electrochemical Hydrogen Production in Water, Chem. Sci, vol.2, pp.1262-1267, 2011.

T. Weber, J. C. Muijsers, and J. W. Niemantsverdriet, Structure of Amorphous MoS 3, J. Phys. Chem, vol.99, pp.9194-9200, 1995.

A. L. Souza, G. Tremiliosi-filho, L. T. Kubota, R. K. Mendes, A. M. Botelho-do-rego et al., Dimethylsiloxane) as a Pre-Coating in Layer-by-Layer Films Containing Phosphotungstate Nanoclusters Electrochemically Sensitive Toward s-Triazines, vol.4, pp.29612-29621, 2014.

Z. Yi, X. Cui, X. Zhang, Y. Chen, J. Xu et al., A Novel 2D Layer Structural Compound Constructed from Tetra-Capped Pseudo-Keggin Heteropolytungstates interacting with Copper Coordination Fragments

, Inorg. Chem

. Commun, , vol.10, pp.1448-1452, 2007.

W. Chen, H. Li, X. Wang, K. Shao, Z. Su et al., Assembly of Cerium(III)-Stabilized Polyoxotungstate Nanoclusters with SeO 3 2-/TeO 3 2-Templates: From Single Polyoxoanions to Inorganic Hollow Spheres in Dilute Solution, Chem. Eur. J, vol.19, pp.11007-11015, 2013.

X. , Photoelectron Spectroscopy Database, NIST Standard Reference Database, vol.20, 2012.

W. N. Isahak, Z. A. Ramli, M. Ismail, and M. A. Yarmo, Highly Selective Glycerol Esterification over Silicotungstic Acid Nanoparticles on Ionic Liquid Catalyst, Ind. Eng. Chem. Res, vol.53, pp.10285-10293, 2014.

C. P. Andrieux and J. Savéant, Molecular Design of Electrode Surfaces

R. W. Murray and . Ed, Techniques of Chemistry Series, vol.XXII, pp.207-270, 1992.

J. C. Gustafsson, B. Liedberg, and O. Inganäs, 4-Ethylenedioxythiophene) Electrode in a Solid State Electrochemical Cell, Situ Spectroscopic Investigations of Electrochromism and Ion Transport in a Poly, vol.3, pp.145-152, 1994.

D. M. Andoshe, S. Choi, Y. Shim, S. H. Lee, Y. Kim et al., A Wafer-Scale Antireflective Protection Layer of Solution-Processed TiO 2 Nanorods for High Performance Silicon-Based Water Splitting Photocathodes, J. Mater. Chem. A, vol.4, pp.9477-9485, 2016.

J. Oh, T. G. Deutsch, H. Yuan, and H. M. Branz, Nanoporous Black Silicon Photocathode for H2 Production by Photoelectrochemical Water Splitting, Energy Environ. Sci, vol.4, pp.1690-1694, 2011.