WO3/CuWO4 Ratio Controls Open-Circuit Photovoltage and Photocurrent in Type II Heterojunction Solar Fuel Photoelectrodes

Escaliante, Lucas Caniati; Azevedo Neto, Nilton Francelosi; Mendoza, Hervin Errol; Xiao, Chengcan; Kandel, Rajesh; da Silva, Jose Humberto Dias; Osterloh, Frank E.

doi:10.1021/acsaem.5c00160

WO₃/CuWO₄ Ratio Controls Open-Circuit Photovoltage and Photocurrent in Type II Heterojunction Solar Fuel Photoelectrodes

Journal Article · Wed Feb 19 00:00:00 EST 2025 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.5c00160· OSTI ID:3005193

^[1]; Azevedo Neto, Nilton Francelosi ^[2]; ^[3]; Xiao, Chengcan ^[3]; Kandel, Rajesh ^[3]; da Silva, Jose Humberto Dias ^[1]; ^[3]

Universidade Estadual Paulista − UNESP, Sao Paulo (Brazil)
Instituto de Tecnologia Aeronáutica − ITA, São Paulo (Brazil)
University of California, Davis, CA (United States)

WO₃/CuWO₄ photoelectrodes for the oxygen evolution reaction benefit from a type II heterojunction for charge separation. However, the impact of the WO₃/CuWO₄ ratio on the photocurrent and the photovoltage is not clear. To probe the effect of composition, Cu_xW_1-xO_y thin films with variable W:Cu ratio were prepared on FTO by reactive magnetron co-sputtering of W and Cu, followed by air annealing at 500ºC. EDS, XRD, Rietveld refinement, and Raman spectroscopy confirm the presence of crystalline WO₃ and CuWO₄ in the W rich films and increasing amounts of amorphous copper oxides in the Cu rich films. Bandgaps were determined by optical absorption spectroscopy, surface photovoltage spectroscopy (SPS), and photoaction spectra and are found to decrease from 2.7 eV to 1.2 eV with increasing copper oxide content. SPS reveals n-type semiconductor photoanode behavior for WO₃/CuWO₄ samples and p-type photocathode behavior for CuO_x rich films. Photoelectrochemical experiments confirm stable water oxidation with Faraday efficiency near unity for all W rich films and photocurrents that are increasing with CuWO₄ content. Optimal performance is seen for WO₃/CuWO₄ mixed phases containing 47-75 mass% CuWO₄. These compositions maximize charge separation at the type II heterojunction interface between the two materials. Additionally, according to incident photon to current efficiency (IPCE) data, the WO₃ improves photon conversion below 350 nm, while CuWO₄ improves conversion at 450-525 nm. Overall, this work shows for the first time how the WO₃/CuWO₄ ratio controls the photovoltage and the photocurrent in type II heterojunction solar fuel photoelectrodes, and how copper oxides in the copper rich films severely degrade the performance. Furthermore, these results are useful in the context of bulk-heterojunction electrodes for the conversion of solar energy into fuels.

View Accepted Manuscript (DOE)

Research Organization:: University of California, Davis, CA (United States)

Sponsoring Organization:: Fundação de Amparo à Pesquisa do Estado de São Paulo – FAPESP; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0015329

Other Award/Contract Number:: 2022/06542-9
2023/022268-2
2023/04793-7

OSTI ID:: 3005193

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 5 Vol. 8; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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