Severe photogenerated charge carrier recombination involved in photocatalytic CO reduction leads to low photocatalytic efficiency. Here we demonstrate that a chiral hierarchical structure could facilitate charge separation in BiOBr, thus suppressing charge recombination and enhancing photocatalytic performance. Chiral helical flower-like BiOBr nanospheres were prepared a D/L-sorbitol-assisted hydrothermal process, exhibiting a 1.1-fold increase in photocatalytic CO reduction activity compared to the achiral counterparts. This enhancement is attributed to the chiral-induced electron spin polarization regulation, as confirmed by photoluminescence and electrochemical characterizations. This work opens an alternative avenue for the design of high-performance photocatalysts.
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http://dx.doi.org/10.1039/d4cc06009a | DOI Listing |
Nanoscale
January 2025
Centre for Nano Science and Nano Technology, S 'O' A (Deemed to be University), Bhubaneswar-751 030, Odisha, India.
Titanium (Ti)-based MOFs are promising materials known for their porosity, stability, diverse valence states, and a lower conduction band (CB) than Zr-MOFs. These features support stable ligand-to-metal charge transfer (LMCT) transitions under photoirradiation, enhancing photocatalytic performance. However, Ti-MOF structures remain a challenge owing to the highly volatile and hydrophilic nature of ionic Ti precursors.
View Article and Find Full Text PDFChem Sci
January 2025
Chemistry and Physics of Materials Unit, School of Advanced Materials (SAMat), Jawaharlal Nehru Centre for Advanced Scientific Research Jakkur Bangalore 560064 India https://www.jncasr.ac.in/faculty/tmaji.
Coordination-driven metallo-supramolecular polymers hold significant potential as highly efficient catalysts for photocatalytic CO reduction, owing to the covalent integration of the light harvesting unit, catalytic center and intrinsic hierarchical nanostructures. In this study, we present the synthesis, characterization, and gelation behaviour of a novel low molecular weight gelator (LMWG) integrating a benzo[1,2-:4,5-']dithiophene core with terpyridine (TPY) units alkyl amide chains (TPY-BDT). The two TPY ends of the TPY-BDT unit efficiently chelate with metal ions, enabling the formation of a metallo-supramolecular polymer that brings together the catalytic center and a photosensitizer in close proximity, maximizing catalytic efficiency for CO reduction.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Department of Chemistry, Institute of Technology Delhi, Hauz Khas, New Delhi 110-016, India.
Pyridinium salts are amine surrogates that are abundant in nature and the redox active nature of the pyridinium salts allows them to serve as precursors for generating radical species under mild conditions that can be initiated by light, heat or metal catalysis. The stereoselective formation of products has always been a topic of interest for synthetic chemists worldwide. In this context, pyridinium salts can readily undergo single electron reduction to form a neutral radical, and the N-X bond's subsequent fragmentation furnishes the X radical without any harsh reaction conditions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Shanghai Institute of Ceramics Chinese Academy of Sciences, State Key Laboratory of High Performance Ceramics and Superfine Microstructure, CHINA.
Pairing photocatalytic 1,2,3,4-tetrahydroisoquinoline semi-dehydrogenation reaction (THIQ-SDR) with two-electron oxygen reduction reaction (2e- ORR) is a green solar to chemical strategy by simultaneously utilizing the photo-excited electrons and holes. However, it is still short of high-efficiency photocatalyst to drive two reactions above. In the present work, crystalline pyrene-thiourea/urea covalent organic frameworks (COF-Py-S and -O) were synthesized and demonstrated as high-performance metal-free photocatalysts.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
State Key Laboratory of Bioinspired Interfacial Materials Science, Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou 215123, China.
Heterogeneity engineering provides an effective route to manipulate the chemical and physical properties of covalent organic frameworks (COFs) but is still under development for their single-crystal form. Here, we report the strategy based on a combination of the template-assisted modulated synthesis with a one-pot crystallization-reduction method to directly construct ordered macro-microporous single crystals of an amine-linked three-dimensional (3D) COF (OM-COF-300-SR). In this strategy, the colloidal crystal-templating synthesis not only assists the formation of ordered macropores but also greatly facilitates the in situ conversion of linkages (from imine to amine) in the COF-300 single crystals.
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