Halide perovskites have garnered significant attention for their unique optoelectronic properties in solar-to-fuel conversions. However, the efficiency of halide perovskites in the field of photocatalytic CO reduction is largely limited by serious charge recombination and a lack of efficient active sites. In this work, a rubidium (Rb) doped CsAgBiBr (Rb:CABB) hierarchical microsphere is developed for photocatalytic CO reduction. Experimental and theoretical analysis discloses that partially substituting Rb for Ag can effectively modulate the electronic structure of CABB, favoring charge separation and making adjacent Bi atoms an electron-rich active site. Further investigations indicated that Rb doping also reduces the energy barriers of the rate-determining step in CO reduction. As a result, Rb:CABB demonstrated an enhanced CO yield compared to its undoped counterpart. This work presents a promising approach to optimizing the electronic structures of photocatalysts and paving a new way for exploring halide perovskites for photocatalytic CO reduction.
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http://dx.doi.org/10.1002/smll.202401202 | DOI Listing |
Adv Mater
January 2025
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012, China.
The design and synthesis of metal-organic frameworks (MOFs) with outstanding light-harvesting and photoexcitation for artificial photocatalytic CO reduction is an attractive but challenging task. In this work, a novel aggregation-induced emission (AIE)-active ligand, tetraphenylpyrazine (PTTBPC) is proposed and utilized for the first time to construct a Zr-MOF photocatalyst via coordination with stable Zr-oxo clusters. Zr-MOF is featured by a scu topology with a two-fold interpenetrated framework, wherein the PTTBPC ligands enable strong light-harvesting and photoexcitation, while the Zr-oxo clusters facilitate CO adsorption and activation, as well as offer potential sites for further metal modification.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Hefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China.
The local electric field (LEF) plays an important role in the catalytic process; however, the precise construction and manipulation of the electric field microenvironment around the active site remains a significant challenge. Here, we have developed a supramolecular strategy for the implementation of a LEF by introducing the host macrocycle 18-crown-6 (18C6) into a cobalt phthalocyanine (CoPc)-containing covalent organic framework (COF). Utilizing the supramolecular interaction between 18C6 and potassium ion (K), a locally enhanced K concentration around CoPc can be built to generate a LEF microenvironment around the catalytically active Co site.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Shanxi Coal International Energy Group Co., Ltd., Taiyuan 030000, China.
Photocatalytic reduction of CO will play a major role in future energy and environmental crisis. To investigate the adsorption mechanisms of CO and HO molecules involved in the catalytic process on the surface of anatase titanium dioxide 101 (TiO(101)) and the influence of Au atom doping on their adsorption, first-principles density functional theory calculations were used. The results show that 1.
View Article and Find Full Text PDFInorg Chem
January 2025
Research Laboratory of Advanced Water and Wastewater Treatment Processes, Department of Applied Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51666-16471, Iran.
In the field of solar energy storage, photocatalytic ammonia production is a next-generation technology. The rapid recombination of charges and insignificant utilization of the sunlight spectrum are bottlenecks of effective photocatalytic N fixation. The introduction of impurities in the crystal lattice and the development of heterojunctions could effectively segregate carriers and improve the solar-light-harvesting capability, which can boost NH generation.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Nankai University, Department of Chemistry, Weijin road, 300071, Tianjin, CHINA.
Localized surface plasmon resonance (LSPR) metals exhibit remarkable light-absorbing property and unique catalytic activity, attracting significant attention in photocatalysts recently. However, the practical application of plasmonic nanometal is hindered by challenge of energetic electrons extraction and low selectivity. The energetic carriers generated in nanometal under illumination have extremely short lifetimes, leading to rapid energy loss.
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