4.7 Article

Inverse Opal CuBi2O4 Photocathodes for Robust Photoelectrochemical Water Splitting

Journal

ACS APPLIED ENERGY MATERIALS
Volume 5, Issue 5, Pages 6050-6058

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsaem.2c00469

Keywords

photoelectrochemical water splitting; CuBi2O4; inverse opal-like structure; photocathode; charge transport

Funding

  1. National Research Foundation of Korea (NRF) - Korean Government [2022R1A2C3003081, 2020H1D3A1A02081461, 2020R1A4A1017737]
  2. NRF grants - Korean Government [2018H1A2A1060233]
  3. Defence Research and Development Organisation (DRDO), ERIPR, India [ERIP/ER/202110001/M01/1788]
  4. Department of Science and Technology (DST), New Delhi, Government of India [IFA19-MS160]
  5. National Research Foundation of Korea [2020H1D3A1A02081461, 2022R1A2C3003081, 2018H1A2A1060233] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)

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This paper introduces an inverse opal-like structured photocathode fabricated using a layered self-assembly approach for photoelectrochemical water-splitting cells. The photocathode has an interconnected macroporous structure that enhances visible-light-harvesting capabilities and improves charge-carrier transport properties. The optimized photocathodes showed high photocurrent density and stability, as well as exceptional photon harvesting and quantum yields.
In general, p-type CuBi2O4 (CBO) photocathodes demonstrate excellent solar-to-hydrogen conversion efficiencies but have low quantum yields near the band-edge region (i.e., above 600 nm), which substantially impedes achieving photocurrent densities that match the theoretical values. This is the main obstacle in the construction of photoelectrochemical (PEC) water-splitting cells. To overcome this difficulty, we fabricated inverse opal-like structured CBO (IO-CBO) photocathodes using a layered self-assembly approach. The fabricated photocathodes have an interconnected macroporous structure that supports enhanced visible-light-harvesting capabilities and improves intrinsic charge-carrier transport properties. Optimized IO-CBO cathodes exhibit a high photocurrent density of 2.95 mA cm(-2) at 0.6 V versus a reversible hydrogen electrode with stability over 2 h of operation. Furthermore, IO-CBO cathodes have exceptional near-band-edge photon harvesting and quantum yields of 15% at 600 nm, which is unprecedented for CuBi2O4 -type photocathodes. We believe that the present work promotes the application of ternary-based nanostructures in solar-driven hydrogen production.

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