Journal of Energy Chemistry
·
2024
·
IF 14
Zhijie Zhang,Xuesheng Wang,Junyi Qian,Jiayue Xu
Heterojunction construction, especially S-scheme heterojunction, represents an efficient universal strategy to achieve high-performance photocatalytic materials. For further performance stimulation of these well-designed heterojunctions, modulating the interfacial internal electric field (IEF) to steer dynamic charge transfer represents a promising approach. Herein, we realized the precise regulation of Fermi level ( E F ) of the oxidation semiconductor (mesoporous WO 3− x ) by tailoring the concentration of oxygen vacancies (V O ), maximizing the IEF intensity in Cs 2 CuBr 4 @WO 3− x (CCB@WO 3− x ) S-scheme heterojunction. The augmented IEF affords a robust driving force for directional electron delivery, leading to boosted charge separation. Hence, the developed CCB@WO 3− x S-scheme heterojunction demonstrated outstanding photocatalytic CO 2 reduction performance, with the electron consumption rate ( R electron ) up to 390.34 μmol g −1 h −1 , which is 3.28 folds higher than that of pure CCB. An in-depth analysis of the S-scheme electron transfer mode was presented via theoretical investigations, electron spin resonance (ESR), photo-irradiated Kelvin probe force microscopy (KPFM), and in-situ X-ray photoelectron spectroscopy (XPS). Finally, the CO 2 photoconversion route was explored in detail using in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and DFT theoretical calculations.
研究领域:
材料科学
·
环境科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Junyi Qian,Hao Hu,Ying Liang,Zhijie Zhang
Halide perovskite quantum dots (PQDs) have shown great promise for the photochemical conversion of CO 2 . However, the fast carrier recombination rates and inadequate adsorption/activation for CO 2 molecules have seriously restricted their practical application. Herein, an innovative step-scheme-based Cs 2 CuBr 4 /TiO 2 (CCB/TiO 2 ) photocatalyst was prepared by embedding Cs 2 CuBr 4 PQDs in a mesoporous TiO 2 matrix, which exhibits considerable potential as candidates for CO 2 photoreduction under simulated sunlight. Remarkably, the optimised CCB/TiO 2 photocatalyst delivered an impressive CO 2 reduction activity, which was 3.1 and 16.0 times higher than those achieved by pure Cs 2 CuBr 4 and TiO 2 , respectively. Furthermore, the S-scheme charge transfer mode was comprehensively corroborated by density functional theory (DFT) calculations, photo-assisted Kelvin probe force microscopy (KPFM), in situ irradiated X-ray photoelectron spectra (XPS), and electron spin resonance spectroscopy (ESR). On basis of theoretical calculations and in situ diffuse reflectance spectra (DRIFTS), the CCB/TiO 2 exhibited a reduced energy barrier of the rate-determining step, which facilitated the CO 2 photoreduction reaction.
研究领域:
材料科学
·
环境科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2022
·
IF 13.7
Jianping Sheng,Ye He,Ming Huang,Chaowei Yuan,Shengyao Wang,Fan Dong
Lead (Pb) halide perovskite quantum dots (PQDs) are promising candidates for the photochemical reduction of CO2. However, the intrinsically weak adsorption and activation toward inert CO2 molecules have seriously hindered their practical application. This study reports alternative Cs2CuBr4 PQDs for gas–solid phase photocatalytic CO2 reduction under simulated solar irradiation. Cs2CuBr4 PQDs exhibited CO2 photoreduction performance with CH4 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 Cs2CuBr4 PQDs induced by surface-frustrated Lewis pair-like properties and intrinsic Cu d-band properties facilitated robust CO2 adsorption and activation. This study demonstrated the potential of Cs2CuBr4 PQDs as a platform for highly efficient CO2 photoreduction and provided a distinct concept for CO2 adsorption and activation based on the catalytic mechanism of Cu-based PQDs.
研究领域:
材料科学
·
环境科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Hao Zheng,Jinlin Yin,Ping Lu,Yi Lu,Xinyan Jiang,Shaoke Chen,Yifei Pan,Ning Zhang,Jin Wang,Zhengquan Li
Fe 2+ -doped Cs 2 CuBr 4 induces strong spin polarization, resulting in efficient charge separation. • O 2 is efficiently activated through antiferromagnetic coupling upon spin-polarized Fe 2+ centers. • The optimized Fe-doped Cs 2 CuBr 4 enables highly efficient and selective photocatalytic oxidation of toluene to benzaldehyde. The high thermodynamic stability and spin-forbidden transition of ground-state triplet oxygen ( 3 O 2 ) to reactive species like superoxide radical (•O 2 − ) pose a formidable challenge for the photocatalytic oxidation of toluene. In this work, we introduced Fe 2+ active sites into Cs 2 CuBr 4 to achieve highly efficient and selective photocatalytic oxidation of toluene to benzaldehyde. The magnetic coupling between Fe 2+ and Cu 2+ breaks the intrinsic antiferromagnetic ordering of the lattice, significantly enhancing spin polarization. Crucially, this enhanced spin state not only facilitates the separation of photogenerated charge carriers but also directly drives the otherwise spin-forbidden conversion of 3 O 2 into reactive oxygen species ( e.g. , •O 2 − ). As a result, the Fe-doped Cs 2 CuBr 4 delivers a dramatically improved benzaldehyde production rate of 15.88 mmol g −1 h −1 (86.4% selectivity), far surpassing the pristine Cs 2 CuBr 4 (0.34 mmol g −1 h −1 ). More strikingly, the application of a 50 mT magnetic field triggers an additional boost to 27.23 mmol g −1 h −1 . This work highlights spin-polarization engineering as an effective strategy for advancing the efficiency and selectivity of photocatalytic oxidation systems. Download: Download high-res image (153KB) Download: Download full-size image
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2023
·
IF 4.6
Zhijie Zhang,Deben Li,Hao Hu,Yaoqing Chu,Jiayue Xu
Metal halide perovskites (MHPs) are emerging as promising candidates for photocatalytic CO2 conversion. However, their practical application is still restricted by the poor intrinsic stability and weak adsorption/activation toward CO2 molecules. The rational design of MHPs-based heterostructures with high stability and abundant active sites is a potential solution to this obstacle. Herein, we report the in situ growth of lead-free Cs2CuBr4 perovskite quantum dots (PQDs) in KIT-6 mesoporous molecular sieve, obtaining remarkable photocatalytic CO2 reduction activity and durable stability. The optimized Cs2CuBr4@KIT-6 heterostructure exhibits the photocatalytic CO and CH4 evolution rates of 51.6 and 17.2 μmol g–1 h–1, respectively, far exceeding those of pristine Cs2CuBr4. On the basis of in situ diffuse reflectance infrared Fourier transform spectra and theoretical investigations, the detailed CO2 photoreduction pathway is systematically revealed. This work provides a new route for the rational construction of perovskite-based heterostructures with strong CO2 adsorption/activation and good stability for photocatalytic CO2 reduction.
研究领域:
材料科学
·
环境科学
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）