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Tailoring S-H Binding Strength of a Sulfur-Rich NiS Cocatalyst for Boosting Visible Light Driven Photocatalytic H2 Production
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  • Khakemin Khan,
  • Zia Ur Rehman,
  • Shanshan Yao,
  • Mohsan Nawaz,
  • Michele Orlandi,
  • Antonio Miotello,
  • Mazhar Ullah,
  • Kifayat Ullah,
  • Abdulaziz Alanazi,
  • Magdi Zaki
Khakemin Khan
University of Trento
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Zia Ur Rehman
Jiangsu University

Corresponding Author:[email protected]

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Shanshan Yao
Jiangsu University
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Mohsan Nawaz
Hazara University Mansehra
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Michele Orlandi
University of Trento
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Antonio Miotello
University of Trento
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Mazhar Ullah
Islamia College Peshawar
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Kifayat Ullah
COMSATS University Islamabad
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Abdulaziz Alanazi
Prince Sattam bin Abdulaziz University
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Magdi Zaki
Imam Muhammad Ibn Saud Islamic University
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Abstract

Transition-metal chalcogenides (MSx) have been shown to be promising low-cost cocatalysts for photocatalytic H2 production. Their performance as cocatalysts, however, is limited due to lack of exposed sulfur (S) sites due to their strong binding with adsorbed atomic hydrogen (S-H). To address this issue, Herein, we demonstrate a unique approach via surface doping of phosphorus (P) atoms into CdS nanorods and fabricated NiS on CdS-P to maintain active site-electron enriched control and electronic structural modification of active S sites. Such a simple nanostructured design exhibits a remarkable improvement in photocatalytic H2 production as 44.39 mmol g-1h-1 under visible light, with an apparent quantum efficiency of 41% at ~ 420 nm. This enhanced photocatalytic hydrogen evolution has been attributable to the modified internal electric field, which accelerates electrons to the surface of NiS for the reduction of hydrogen into H2 instead of adhering to it. Various characterization, such as XPS demonstrate phosphorous doping play a key role in transferring of free electron from CdS to NiS to induce electron-enriched Sδ- active centers resulting in a decrease S-H binding force and boosting photocatalytic hydrogen production. This work describes a broad method for maintaining the number of active sites while tailoring the binding strength between active sites and hydrogen adsorbates.