Partially Oxidized SnS₂ Atomic Layers Achieving Efficient Visible-Light-Driven CO₂ Reduction

Abstract

Unraveling the role of surface oxide on affecting its native metal disulfide's CO photoreduction remains a grand challenge. Herein, we initially construct metal disulfide atomic layers and hence deliberately create oxidized domains on their surfaces. As an example, SnS atomic layers with different oxidation degrees are successfully synthesized. In situ Fourier transform infrared spectroscopy spectra disclose the COOH* radical is the main intermediate, whereas density-functional-theory calculations reveal the COOH* formation is the rate-limiting step. The locally oxidized domains could serve as the highly catalytically active sites, which not only benefit for charge-carrier separation kinetics, verified by surface photovoltage spectra, but also result in electron localization on Sn atoms near the O atoms, thus lowering the activation energy barrier through stabilizing the COOH* intermediates. As a result, the mildly oxidized SnS atomic layers exhibit the carbon monoxide formation rate of 12.28 μmol g h, roughly 2.3 and 2.6 times higher than those of the poorly oxidized SnS atomic layers and the SnS atomic layers under visible-light illumination. This work uncovers atomic-level insights into the correlation between oxidized sulfides and CO reduction property, paving a new way for obtaining high-efficiency CO photoreduction performances.

Ultrasmall MoOx Clusters as a Novel Cocatalyst for Photocatalytic Hydrogen Evolution

“…TEM images and XRD patterns of CdS/MoO x before and after the reaction show no obvious change, which further demonstrates the high stability of the CdS/MoO x photo catalyst ( Figure S11, Supporting Information). [37] To investigate the recombination behavior of charge carriers, fluorescence decay curves of different samples are collected ( Figure S13, Supporting Information). This phenomenon indicates that the generation of H 2 is driven by photoexcitation.…”

Lattice Distortion in Hollow Multi‐Shelled Structures for Efficient Visible‐Light CO2Reduction with a SnS2/SnO2Junction

“…XRD patterns of hollow spheres, double‐, triple‐, and quadruple‐shelled SnS 2 /SnO 2 heterogeneous HoMSs (Supporting Information, Figure S2) indicate that the products are mixture of hexagonal SnS 2 (JCPDS card no. 23‐677) and tetragonal SnO 2 (JCPDS card no. 21‐1250), and no additional peaks can be detected.…”

“…After obtaining electrons or/and interacting with the surface protons from the dissociating of surface absorbed water molecules, CO 2 − or/and COOH* intermediates formed. Further protonation of COOH* intermediates could product CO* groups, and the last step in the photocatalytic CO 2 process was the desorption of CO* from the catalyst surface …”

A Plasma‐Triggered O−S Bond and P−N Junction Near the Surface of a SnS2 Nanosheet Array to Enable Efficient Solar Water Oxidation

“…[4] As at ypical twodimensional (2D) layered semiconductor,S nS 2 has been explored as an efficient photocatalyst owing to its unique optical and electronic properties. [6] Moreover,SnS 2 has an average carrier diffusion length as long as 0.19 mmt of acilitate the charge transfer. [6] Moreover,SnS 2 has an average carrier diffusion length as long as 0.19 mmt of acilitate the charge transfer.…”