Efficient direct solar-to-hydrogen conversion by in situ interface transformation of a tandem structure

Photosynthesis is nature's route to convert intermittent solar irradiation into storable energy, while its use for an industrial energy supply is impaired by low efficiency. Artificial photosynthesis provides a promising alternative for efficient robust carbon-neutral renewable energy generation. The approach of direct hydrogen generation by photoelectrochemical water splitting utilizes customized tandem absorber structures to mimic the Z-scheme of natural photosynthesis. Here a combined chemical surface transformation of a tandem structure and catalyst deposition at ambient temperature yields photocurrents approaching the theoretical limit of the absorber and results in a solar-to-hydrogen efficiency of 14%. The potentiostatically assisted photoelectrode efficiency is 17%. Present benchmarks for integrated systems are clearly exceeded. Details of the in situ interface transformation, the electronic improvement and chemical passivation are presented. The surface functionalization procedure is widely applicable and can be precisely controlled, allowing further developments of high-efficiency robust hydrogen generators.

[1]  Allen J. Bard,et al.  Artificial Photosynthesis: Solar Splitting of Water to Hydrogen and Oxygen , 1995 .

[2]  G. N. Baum,et al.  Technical and economic feasibility of centralized facilities for solar hydrogen production via photocatalysis and photoelectrochemistry , 2013 .

[3]  H. Lewerenz,et al.  Interface condition of n-Si(111) during photocurrent oscillations in NH4F solutions , 1995 .

[4]  Turner,et al.  A monolithic photovoltaic-photoelectrochemical device for hydrogen production via water splitting , 1998, Science.

[5]  A. Clawson.  Guide to references on III-V semiconductor chemical etching , 2001 .

[6]  H. Lewerenz,et al.  A model for electrochemical oscillations at the Si ∣ electrolyte contact: Part II. Simulations and experimental results , 2000 .

[7]  Ib Chorkendorff,et al.  2-Photon tandem device for water splitting: comparing photocathode first versus photoanode first designs , 2014 .

[8]  D. M. King,et al.  Coulometric Analysis with Gas Volume Measurement , 1964 .

[9]  Joel W. Ager,et al.  Net primary energy balance of a solar-driven photoelectrochemical water-splitting device , 2013 .

[10]  T. Hannappel,et al.  Optical in Situ Study of InP(100) Surface Chemistry: Dissociative Adsorption of Water and Oxygen , 2014 .

[11]  T. Vo‐Dinh,et al.  Photoelectrocatalysis: principles, nanoemitter applications and routes to bio-inspired systems , 2010 .

[12]  D. Gamelin,et al.  Near-complete suppression of surface recombination in solar photoelectrolysis by "Co-Pi" catalyst-modified W:BiVO4. , 2011, Journal of the American Chemical Society.

[13]  J. Joseph,et al.  Passivation of InP using In(PO3)3‐condensed phosphates: From oxide growth properties to metal‐insulator‐semiconductor field‐effect‐transistor devices , 1992 .

[14]  Eric L. Miller,et al.  Photoelectrochemical hydrogen production , 1995 .

[15]  P. Würfel,et al.  Physics of solar cells : from basic principles to advanced concepts , 2009 .

[16]  H. Gerischer,et al.  Underpotential deposition of metals and work function differences , 1974 .

[17]  P. Würfel,et al.  How Solar Cells Work , 2010 .

[18]  H. Queisser,et al.  Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells , 1961 .

[19]  O. Supplie,et al.  The interface of GaP(100) and H2O studied by photoemission and reflection anisotropy spectroscopy , 2013, 1305.5815.

[20]  Silicon based tandem cells: novel photocathodes for hydrogen production. , 2014, Physical chemistry chemical physics : PCCP.

[21]  Nathan S. Lewis,et al.  An analysis of the optimal band gaps of light absorbers in integrated tandem photoelectrochemical water-splitting systems , 2013 .

[22]  H. Gerischer.  Heterogeneous electrochemical systems for solar energy conversion , 1980 .

[23]  Matthew R. Shaner,et al.  Experimental demonstrations of spontaneous, solar-driven photoelectrochemical water splitting , 2015 .

[24]  Michael Grätzel,et al.  Photoelectrochemical Hydrogen Production , 2012 .

[25]  Katherine T Fountaine,et al.  Current-voltage characteristics of coupled photodiode-electrocatalyst devices , 2013 .

[26]  Mohammad Khaja Nazeeruddin,et al.  Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts , 2014, Science.

[27]  A. Bard.  Photoelectrochemistry and heterogeneous photo-catalysis at semiconductors , 1979 .

[28]  Gang Chen,et al.  Structure-sensitive oxidation of the indium phosphide (001) surface , 2002 .

[29]  I. Ial,et al.  Nature Communications , 2010, Nature Cell Biology.

[30]  Frank Dimroth,et al.  Metamorphic GayIn1−yP/Ga1−xInxAs tandem solar cells for space and for terrestrial concentrator applications at C > 1000 suns , 2001 .

[31]  Bruce A. Parkinson,et al.  CHAPTER 1:The Potential Contribution of Photoelectrochemistry in the Global Energy Future , 2013 .

[32]  G. Olah,et al.  Anthropogenic chemical carbon cycle for a sustainable future. , 2011, Journal of the American Chemical Society.

[33]  L. Peter,et al.  Photoelectrochemical water splitting : materials, processes and architectures , 2013 .

[34]  J. Turner,et al.  Electrochemical stability of p-GaInP2 in aqueous electrolytes toward photoelectrochemical water splitting , 1998 .

[35]  M. Seah,et al.  Practical Surface Analysis , 1992 .

[36]  Allen J. Bard,et al.  Electrochemical Methods: Fundamentals and Applications , 1980 .

[37]  Chuan-Jian Zhong,et al.  Core–Shell Assembled Nanoparticles as Catalysts , 2001 .

[38]  T. Hannappel,et al.  Photoelectrochemical Conditioning of MOVPE p-InP Films for Light-Induced Hydrogen Evolution: Chemical, Electronic and Optical Properties , 2013 .

[39]  Jerry R. Meyer,et al.  Band parameters for III–V compound semiconductors and their alloys , 2001 .

[40]  L. Peter,et al.  Surface recombination at semiconductor electrodes: Part II. Photoinduced “near-surface” recombination centres in p-GaP , 1984 .

[41]  Tetsuo Soga,et al.  Over 18% solar energy conversion to generation of hydrogen fuel; theory and experiment for efficient solar water splitting , 2001 .

[42]  A. Fujishima,et al.  Electrochemical Photolysis of Water at a Semiconductor Electrode , 1972, Nature.

[43]  A. Rainoldi,et al.  Part II , 2012 .

[44]  Matthew R. Shaner,et al.  Amorphous TiO2 coatings stabilize Si, GaAs, and GaP photoanodes for efficient water oxidation , 2014, Science.

[45]  W. Jaegermann,et al.  Solar hydrogen generation with wide-band-gap semiconductors: GaP(100) photoelectrodes and surface modification. , 2012, Chemphyschem : a European journal of chemical physics and physical chemistry.

[46]  F. Willig,et al.  In-situ monitoring and analysis of GaSb(100) substrate deoxidation , 2005 .

[47]  E. Schwegler,et al.  Surface Chemistry of GaP(001) and InP(001) in Contact with Water , 2014 .