Pt–Cu Interaction Induced Construction of Single Pt Sites for Synchronous Electron Capture and Transfer in Photocatalysis

Abstract

Single-atom photocatalysts have shown their fascinating strengths in enhancing charge transfer dynamics; however, rationally designing coordination sites by metal doping to stabilize isolated atoms is still challenging. Here, a one-unit-cell ZnIn 2 S 4 (ZIS) nanosheet with abundant Cu dopants serving as the suitable support to achieve a single atom Pt catalyst (Pt 1 /Cu-ZIS) is reported, and hence the metal single atom-metal dopant interaction at an atomic level is disclosed. Experimental results and density functional theory calculations highlight the unique stabilizing effect (Pt-Cu interaction) of single Pt atoms in Cu-doped ZIS, while apparent Pt clusters are observed in pristine ZIS. Specifically, Pt-Cu interaction provides an extra coordination site except three S sites on the surface, which induces a higher diffusion barrier and makes the single atom more stable on the surface. Apart from stabilizing Pt single atoms, Pt-Cu interaction also serves as the efficient channel to transfer electrons from Cu trap states to Pt active sites, thereby enhancing the charge separation and transfer efficiency. Remarkably, the Pt 1 /Cu-ZIS exhibits a superb activity, giving a photocatalytic hydrogen evolution rate of 5.02 mmol g −1 h −1 , nearly 49 times higher than that of pristine ZIS.

Controllable Synthesis of Web‐Footed PdCu Nanosheets and Their Electrocatalytic Applications

“…We infer that the Cu atoms in‐plane region of NSs should originate from the atomic diffusion during the synthetic process. [ 45 ] Rough surfaces with abundant atomic steps/corners can be found at the end of branches (Figure 2e). It is believed that the atomic steps/corners could provide extra catalytic active sites to boost the catalytic current density.…”

Single-atom catalysts for high-efficiency photocatalytic and photoelectrochemical water splitting: distinctive roles, unique fabrication methods and specific design strategies

“…, NPs and SAs) fabricated by the same preparation method. 159 For instance, Su et al reported Cu doping in ZnIn 2 S 4 (ZIS) NSs as substrates to anchor Pt SAs through an infiltration method for photocatalytic water splitting as shown in Fig. 3b.…”

“…Some methods used for NP fabrication can also be employed to prepare SA-based photocatalysts by making some modications. 156,158,159 In these methods, NPs are used as intermediate states that can be transformed into SAs on the surface by special subsequent treatment through reducing the particle size. 158,160 For instance, Cai et al have found that the in situ formed surface OVs on TiO 2 nanobelts promoted the redistribution of Pt NPs as stable Pt SAs.…”

“…It has also been reported that the modication of the substrates (e.g., by doping) had strong inuences on the anchored metal species on the surface (e.g., NPs and SAs) fabricated by the same preparation method. 159 For instance, Su et al reported Cu doping in ZnIn 2 S 4 (ZIS) NSs as substrates to anchor Pt SAs through an inltration method for photocatalytic water splitting as shown in Fig. 3b.…”

“…3b. 159 Pt SAs were isolated and stabilized on the surface of Cu-doped ZIS due to the formation of Pt-Cu interactions while Pt NPs and Pt NCs were formed on the surface of a pristine ZIS substrate without Cu doping via the same impregnation route.…”