Frustrated Lewis Pair Sites Boosting CO₂ Photoreduction on Cs₂CuBr₄ Perovskite Quantum Dots

Abstract

Lead (Pb) halide perovskite quantum dots (PQDs) are promising candidates for the photochemical reduction of CO 2 . However, the intrinsically weak adsorption and activation toward inert CO 2 molecules have seriously hindered their practical application. This study reports alternative Cs 2 CuBr 4 PQDs for gas−solid phase photocatalytic CO 2 reduction under simulated solar irradiation. Cs 2 CuBr 4 PQDs exhibited CO 2 photoreduction performance with CH 4 and CO yields of 74.81 and 148.98 μmol g −1 , respectively. In situ diffuse reflectance infrared Fourier transform spectra and density functional theory calculations cooperatively revealed the synergistic strengthening of microelectronic polarization in Cs 2 CuBr 4 PQDs induced by surface-frustrated Lewis pair-like properties and intrinsic Cu d-band properties facilitated robust CO 2 adsorption and activation. This study demonstrated the potential of Cs 2 CuBr 4 PQDs as a platform for highly efficient CO 2 photoreduction and provided a distinct concept for CO 2 adsorption and activation based on the catalytic mechanism of Cu-based PQDs. KEYWORDS: photocatalytic CO 2 reduction, Cs 2 CuBr 4 , perovskite quantum dots, CO 2 adsorption and activation, catalytic mechanism

Rational Design of Metal Halide Perovskite Nanocrystals for Photocatalytic CO2 Reduction: Recent Advances, Challenges, and Prospects

“…Schematic illustration of possible directions for MHP NCs photocatalysts: constructing a heterojunction at the single-particle level, photocatalytic mechanisms (Inset is reproduced with permission from ref . Copyright 2022 American Chemical Society.…”

“…Cs 2 CuBr 4 possesses strong CO 2 adsorption and activation upon dual-site adsorption (see inset of Figure ). In contrast, CO 2 tended to be adsorbed on the isolated Pb atom site of CsPbBr 3 through single C–Pb adsorption with weak CO 2 adsorption . Our group has also investigated the Δ G of CO 2 reduction on ZnSe and CsSnCl 3 , respectively.…”

“…In contrast, CO 2 tended to be adsorbed on the isolated Pb atom site of CsPbBr 3 through single C−Pb adsorption with weak CO 2 adsorption. 108 Our group has also investigated the ΔG of CO 2 reduction on ZnSe and CsSnCl 3 , respectively. For the rate-determining step of COOH* formation, the ΔG value of ZnSe (1.87 eV) is higher than that of CsSnCl 3 (0.69 eV), suggesting that it is much easier to form the COOH* intermediate on the CsSnCl 3 surface.…”

Inorganic Copper-Based Halide Perovskite for Efficient Photocatalytic CO2 Reduction

“…, with a formula A x Cu y X z (A = Cs + , Rb + , CH 3 NH 2 + , or CH 4 N 2 + ; X = Cl – , Br – , or I – ). − Among them, much attention has been given to Cu + -based halides, which have been demonstrated as good luminescent materials. For Cu 2+ , very recently, Cs 2 CuBr 4 halide was reported as a photocatalyst for the photocatalytic CO 2 reduction reaction . Meanwhile, for CsCuCl 3 with a one-dimensional (1D) chain hexagonal perovskite structure, its narrow bandgap and high thermal stability may render it as a kind of good photoelectric material. , However, there were only a few reports concerning its photoelectric properties and applications, such as photoelectrical detectors and fluorescence sensors for detecting transition metal ions (Fe 2+ , Cr 2+ , Mn 2+ , Pb 2+ , etc .…”

Frustrated Lewis Pairs in Heterogeneous Catalysis: Theoretical Insights

“…As shown in Figure 1, an FLP assembles a Lewis acid (LA) and base (LB) pair in proximity, but with steric hindrance to prevent them from recombining, so as to activate small molecules [26][27][28]. Besides catalyzing heterolytic H 2 dissociation [29,30], FLP catalysts have also been used in the activation of other molecules (e.g., alkenes, aldehydes and CO 2 ) [31][32][33][34][35][36][37], thereby providing a new strategy for synthetic chemistry. Inspired by unique FLP-based catalysts in homogenous catalysis, this concept has recently been extended to heterogeneous catalysis [38,39].…”