Black TiO2–x Nanoparticles Decorated with Ni Nanoparticles and Trace Amounts of Pt Nanoparticles for Photocatalytic Hydrogen Generation

  • Shubham Biswas
    Shubham Biswas
    Department of Chemical Engineering, IIT(ISM) Dhanbad 826004, India
  • Ha-Young Lee
    Ha-Young Lee
    Department of Energy Science and Engineering, DGIST, Daegu 42988, Republic of Korea
    More by Ha-Young Lee
  • Manohar Prasad
    Manohar Prasad
    Department of Chemical Engineering, IIT(ISM) Dhanbad 826004, India
  • Abhishek Sharma
    Abhishek Sharma
    Department of Chemical Engineering, IIT(ISM) Dhanbad 826004, India
  • Jong-Sung Yu
    Jong-Sung Yu
    Department of Energy Science and Engineering, DGIST, Daegu 42988, Republic of Korea
    Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taipei 10607, Taiwan
    More by Jong-Sung Yu
  • Siddhartha Sengupta
    Siddhartha Sengupta
    Department of Chemical Engineering, IIT(ISM) Dhanbad 826004, India
  • Devendra Deo Pathak
    Devendra Deo Pathak
    Department of Applied Chemistry, IIT(ISM) Dhanbad 826004, India
  • , and 
  • Apurba Sinhamahapatra*
    Apurba Sinhamahapatra
    Department of Chemical Engineering, IIT(ISM) Dhanbad 826004, India
    *Email: [email protected]
Cite this: ACS Appl. Nano Mater. 2021, 4, 5, 4441–4451
Publication Date (Web):May 11, 2021
https://doi.org/10.1021/acsanm.0c03484
Copyright © 2021 American Chemical Society
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Abstract

A cocatalyst plays an essential role in photoassisted hydrogen generation, and it is an almost inevitable component of a photocatalyst. Costly noble metal (e.g., Pt) cocatalysts exhibit almost irreplaceable efficiencies, and finding a suitable replacement is a challenging proposition. Controlled synthesis of a nanoparticle cocatalyst on semiconductors at the nanoscale level is one of the most promising approaches to accomplish the Pt equivalent activity. Herein, a photodeposited metallic Ni-based cocatalyst containing a small amount of Pt (<2 atom % with respect to Ni) on reduced/black TiO2–x is introduced. The developed cocatalyst (2.21 wt % Ni and 0.094 wt % Pt with respect to TiO2–x) exhibits better charge separation efficiency and photoassisted hydrogen generation rate than an only-Pt (0.91 wt %) cocatalyst from methanol–water. The rates are 69 and 3.1 mmol g–1 h–1 for a Ni-based cocatalyst, while 65 and 2.5 mmol g–1 h–1 for a Pt cocatalyst, respectively, under ultraviolet–visible and visible light. A small amount of Pt ensures the photodeposition of Ni nanoparticles adjacent to Pt nanoparticles, enhancing the charge migration from the reduced TiO2–x surface for hydrogen evolution. It is found that in the absence of Pt, the photodeposited Ni(OH)2 is obtained instead of metallic Ni nanoparticles, which exhibits a comparatively low hydrogen generation rate. The present study opens an alternative way to cocatalyst design and fabrication by the controlled synthesis of nanoparticles for a wide range of photocatalytic conversions facilitated by enhanced charge separation.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsanm.0c03484.

  • Results obtained and calculated for hydrogen generated over 2.5% Ni-0.1% Pt-BT; comparison of the developed photocatalyst system with the reported systems; plot of generated hydrogen versus time; GC chromatogram for a standard mixture of different gases; GC chromatogram for generated gas during the photocatalytic reaction; characterization results of WT and BT including XRD, Raman, XPS, PL, SEM, TEM, elemental mapping and EDSA; elemental mapping and EDSA results for 2.5% Ni-BT; and H2 generation profile and rate from 10 % methanol–water under ultraviolet–visible light using in situ photodeposited Ni species on BT in the presence of Pt (PDF)

  • H2 generation (MP4)

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