The hydrogen evolution capacity of MoS₂ is impeded by its intrinsically highly electronegative sulfur sites, which firmly bind absorbed atomic H through S–H_ads bonds and subsequently diminish H₂ release. Designing effective surface-active sites to optimize atomic hydrogen activation and desorption for the hydrogen evolution reaction (HER) in water, while also expanding near-infrared (NIR) light responsiveness, remains a significant challenge. We have developed complexes of sulfur vacancy (S_v) enriched CdS_v capped with W-modified MoS_2+x (MoWS_2+x) through an in situ substitution approach, followed by a photoreduction reaction. The bimetallic MoWS_2+x cocatalyst not only increases the density of unsaturated coordinating S active sites but also attenuates the strength of the S–H_ads bond. The optimized MoWS_2+x/CdS_v hybrid shows synergistic improvement of atomic H activation and desorption for the solar-driven HER, achieving the highest recorded H₂-evolution rate of 9166.13 μmol g⁻¹ h⁻¹ under visible light (λ ≥ 420 nm), which marks a substantial improvement (greater than 750%), and an apparent quantum yield of 19.13%. Remarkably, the target photocatalyst, which is abundant in sulfur vacancies within its CdS_v component, also achieves H₂ production driven by NIR light beyond 780 nm, with a H₂ evolution rate of 1326.82 μmol g⁻¹ h⁻¹. Comprehensive experimental and theoretical investigations corroborate that the existence of unsaturated coordinated S sites mitigates the strength of S–H_ads bonds, resulting in the high driving force of H₂ bubble release from water and long-lived active charge carriers. In this paper, we constructed visible light and NIR-active photocatalysts successfully for hydrogen production, highlighting the synergetic effects within this unique system. Additionally, the photo-behaviors of charge carriers have been investigated by ultra-fast spectroscopic techniques to gain a deeper understanding of the interfacial charge transfer kinetics. This study provides valuable insights into the development and optimization of photocatalysts that are responsive to both NIR and visible light, paving the way for more efficient solar-driven applications.

中文翻译：

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增强的光催化 H2 析出：在空位工程 CdS 晶体上，通过富硫 MoWS2+x 中的自由电子转移优化原子氢解吸


MoS₂ 的析氢能力受到其固有的高电负性硫位点的阻碍，该位点通过 S-H_ads 键牢固地结合吸收的原子 H，随后减少 H₂ 的释放。设计有效的表面活性位点以优化水中析氢反应 （HER） 的氢原子活化和解吸，同时扩大近红外 （NIR） 光响应能力，仍然是一项重大挑战。我们通过原位取代方法开发了富含硫空位 （S_v） 的 CdS_v 的复合物，该复合物用 W 修饰的 MoS_2+x （MoWS_2+x） 封端，然后进行光还原反应。双金属 MoWS_2+x 助催化剂不仅增加了不饱和配位 S 活性位点的密度，而且还减弱了 S-H_ads 键的强度。优化的 MoWS_2+x/CdS_v 杂化物显示出太阳能驱动 HER 的原子 H 活化和解吸的协同改善，在可见光 （λ ≥ 420 nm） 下实现了 9166.13 μmol ^{g-1 h-1} 的最高记录 H₂ 析出率，这标志着显着改进（大于 750%），表观量子产率为 19.13%。 值得注意的是，在其 CdS_v 组分中富含硫空位的靶光催化剂也实现了由 780 nm 以上的 NIR 光驱动的 H₂ 产生，H₂ 析出速率为 1326.82 μmol ^{g-1 h-1}。全面的实验和理论研究证实，不饱和配位 S 位点的存在减轻了 S-H_ads 键的强度，导致 H₂ 气泡从水中释放的高驱动力和长寿命的活性电荷载流子。在本文中，我们成功地构建了用于制氢的可见光和 NIR 活性光催化剂，突出了这个独特系统内的协同效应。此外，通过超快光谱技术研究了电荷载流子的光行为，以更深入地了解界面电荷转移动力学。这项研究为开发和优化对 NIR 和可见光都有响应的光催化剂提供了有价值的见解，为更高效的太阳能驱动应用铺平了道路。