Delocalized Orbitals over Metal Clusters and Organic Linkers Enable Boosted Charge Transfer in Metal–Organic Framework for Overall CO2 Photoreduction DOI
Haixiong Liu, Zijian Zhou, Lei Xie

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(47)

Опубликована: Июль 17, 2024

Abstract The conversion of CO 2 to C through photocatalysis poses significant challenges, and one the biggest hurdles stems from sluggishness multi‐electron transfer process. Herein, taking metal–organic framework (MOF, PFC‐98) as a model photocatalyst, we report new strategy facilitate charge separation. This involves matching energy levels lowest unoccupied node linker orbitals MOF, thereby creating crystal orbital (LUCO) delocalized over both linker. feature enables direct excitation electrons photosensitive catalytic centers, achieving (DCT) pathway. For comparison, an isoreticular MOF (PFC‐6) based on analogue components but with far apart frontier level was synthesized. LUCO caused presence internal charge‐separated (ICS) state, prolonging excited state lifetime further inhibiting electron‐hole recombination. ICS prolongs inhibits Moreover, it also induced abundant accumulating at sites, enabling As result, material featuring exhibits superior overall photocatalytic performance high production yield selectivity.

Язык: Английский

Oxygen-tolerant CO2 electroreduction over covalent organic frameworks via photoswitching control oxygen passivation strategy DOI Creative Commons

Hong‐Jing Zhu,

Duan‐Hui Si, Hui Guo

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Фев. 17, 2024

Abstract The direct use of flue gas for the electrochemical CO 2 reduction reaction is desirable but severely limited by thermodynamically favorable oxygen reaction. Herein, a photonicswitching unit 1,2-Bis(5’-formyl-2’-methylthien-3’-yl)cyclopentene (DAE) integrated into cobalt porphyrin-based covalent organic framework highly efficient electrocatalysis under aerobic environment. DAE moiety in material can reversibly modulate O activation capacity and electronic conductivity ring-closing/opening reactions UV/Vis irradiation. DAE-based with ring-closing type shows high Faradaic efficiency 90.5% partial current density −20.1 mA cm −2 at −1.0 V vs. reversible hydrogen electrode co-feeding 5% . This work presents an passivation strategy to realize electroreduction performance , which would inspire design electrocatalysts practical source such as from power plants or air.

Язык: Английский

Процитировано

57
Covalent Organic Frameworks for Photocatalytic Reduction of Carbon Dioxide: A Review DOI
Jinglun Yang, Zihao Chen, Lei Zhang

и другие.

ACS Nano, Год журнала: 2024, Номер 18(33), С. 21804 - 21835

Опубликована: Авг. 8, 2024

Covalent organic frameworks (COFs) are crystalline networks with extended backbones cross-linked by covalent bonds. Due to the semiconductive properties and variable metal coordinating sites, along rapid development in linkage chemistry, utilization of COFs photocatalytic CO2RR has attracted many scientists' interests. In this Review, we summarize latest research progress on for CO2 reduction. first part, present COF linkages that have been used CO2RR, discuss four mechanisms including as intrinsic photocatalysts, photosensitive motifs metalated semiconductors heterojunction photocatalysts. Then, principles structural designs functional building units stacking mode exchange. Finally, outlook challenges provided. This Review is intended give some guidance design synthesis diverse different linkages, various structures, divergent modes efficient photoreduction CO2.

Язык: Английский

Процитировано

34
Elaborate Modulating Binding Strength of Intermediates via Three‐component Covalent Organic Frameworks for CO2 Reduction Reaction DOI
Minghao Liu, Cheng‐Xing Cui, Shuai Yang

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(20)

Опубликована: Фев. 26, 2024

Abstract The catalytic performance for electrocatalytic CO 2 reduction reaction (CO RR) depends on the binding strength of reactants and intermediates. Covalent organic frameworks (COFs) have been adopted to catalyze RR, their abilities are tuned via constructing donor‐acceptor (DA) systems. However, most DA COFs single donor acceptor units, which caused wide‐range but lacking accuracy in modulating More elaborate regulation interactions with intermediates necessary challenge construct high‐efficiency catalysts. Herein, three‐component COF D‐A‐A units was first constructed by introducing electron‐rich diarylamine unit, electron‐deficient benzothiazole Co‐porphyrin units. Compared two‐component COFs, designed exhibit elevated electronic conductivity, enhanced reducibility, high efficiency charge transfer, further improving RR faradic 97.2 % at −0.8 V activity partial current density 27.85 mA cm −2 −1.0 exceed other COFs. Theoretical calculations demonstrate that sites suitable ability intermediates, benefit formation *COOH desorption *CO. This work offers valuable insights advancement multi‐component enabling modulated transfer improve activity.

Язык: Английский

Процитировано

22
Covalent-Metal organic Frameworks: Preparation and applications DOI
Zhaobo Wang, Chen Wang, Qiming Hu

и другие.

Chemical Engineering Journal, Год журнала: 2024, Номер 483, С. 149217 - 149217

Опубликована: Фев. 2, 2024

Язык: Английский

Процитировано

18
Recent Advances and Challenges in Efficient Selective Photocatalytic CO2 Methanation DOI

Piyan Wang,

Fengyi Yang, Jiafu Qu

и другие.

Small, Год журнала: 2024, Номер 20(32)

Опубликована: Март 15, 2024

Abstract Solar‐driven carbon dioxide (CO 2 ) methanation holds significant research value in the context of emission reduction and energy crisis. However, this eight‐electron catalytic reaction presents substantial challenges activity selectivity. In regard, researchers have conducted extensive exploration achieved developments. This review provides an overview recent advances efficient selective photocatalytic CO methanation. It begins by discussing fundamental principles detail, analyzing strategies for improving efficiency conversion to CH 4 comprehensively. Subsequently, it outlines applications advanced characterization methods Finally, highlights prospects opportunities area, aiming inspire into high‐value shed light on mechanisms.

Язык: Английский

Процитировано

18
Microenvironment Engineering of Heterogeneous Catalysts for Liquid-Phase Environmental Catalysis DOI

Zhong‐Shuai Zhu,

Shuang Zhong, Cheng Cheng

и другие.

Chemical Reviews, Год журнала: 2024, Номер 124(20), С. 11348 - 11434

Опубликована: Окт. 9, 2024

Environmental catalysis has emerged as a scientific frontier in mitigating water pollution and advancing circular chemistry reaction microenvironment significantly influences the catalytic performance efficiency. This review delves into engineering within liquid-phase environmental catalysis, categorizing microenvironments four scales: atom/molecule-level modulation, nano/microscale-confined structures, interface surface regulation, external field effects. Each category is analyzed for its unique characteristics merits, emphasizing potential to enhance efficiency selectivity. Following this overview, we introduced recent advancements advanced material system design promote (e.g., purification, transformation value-added products, green synthesis), leveraging state-of-the-art technologies. These discussions showcase was applied different reactions fine-tune regimes improve from both thermodynamics kinetics perspectives. Lastly, discussed challenges future directions engineering. underscores of intelligent materials drive development more effective sustainable solutions decontamination.

Язык: Английский

Процитировано

14
Reticular Materials for Photocatalysis DOI
Kang Sun, Yunyang Qian, Dandan Li

и другие.

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 27, 2024

Abstract Photocatalysis leverages solar energy to overcome the thermodynamic barrier, enabling efficient chemical reactions under mild conditions. It can greatly reduce reliance on traditional sources and has attracted significant research interest. Reticular materials, including metal‐organic frameworks (MOFs) covalent organic (COFs), represent a class of crystalline materials constructed from molecular building blocks linked by coordination bonds, respectively. function as heterogeneous catalysts, combining well‐defined structures high tailorability akin homogeneous catalysts. In this review, regulation light absorption, charge separation, surface in photocatalytic process through precise molecular‐level design based features reticular is elaborated. Notably, for MOFsmicroenvironment modulation around catalytic sites affects performance delved, with emphasis their unique dynamic flexible microenvironments. For COFs, inherent excitonic effects due fully nature discussed highlight strategies regulate charge‐ and/or energy‐transfer‐mediated photocatalysis. Finally, current challenges future directions field, aiming provide comprehensive understanding how be optimized enhanced photocatalysis discussed.

Язык: Английский

Процитировано

11
Modulation of Electrochemical Reactions through External Stimuli: Applications in Oxygen Evolution Reaction and Beyond DOI
Baoshan Liu, Haoyin Zhong, Jing Liu

и другие.

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Янв. 29, 2025

Electrochemical water splitting is a promising method for generating green hydrogen gas, offering sustainable approach to addressing global energy challenges. However, the sluggish kinetics of anodic oxygen evolution reaction (OER) poses great obstacle its practical application. Recently, increasing attention has been focused on introducing various external stimuli modify OER process. Despite significant enhancement in catalytic performance, an in-depth understanding origin superior activity contributed by remains elusive, which significantly hinders further development highly efficient and durable electrolyzed devices. Herein, this review systematically summarizes recent advancements stimuli, including photon irradiation, applied magnetic field, thermal heating, etc., boost activities. In particular, underlying mechanisms promote species transfer, electronic structure electrocatalysts, accelerate structural reconstruction are highlighted. Additionally, applications other electrocatalytic reactions also presented. Finally, several remaining challenges future opportunities discussed, providing insights that could study support rational design storage conversion

Язык: Английский

Процитировано

2
Porphyrin‐Based Covalent Organic Frameworks for CO2 Photo/Electro‐Reduction DOI Open Access

Sun Tingting,

Zhi Wang, Yuhui Wang

и другие.

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Фев. 9, 2025

Photo/electro-catalytic CO2 reduction into high-value products are promising strategies for addressing both environmental problems and energy crisis. Duo to their advantageous visible light absorption ability, adjustable optic/electronic properties, definite active center, post-modification capability, excellent stability, porphyrin-based covalent organic frameworks (COFs) have emerged as attractive photo/electro-catalysts towards reduction. In this review, the research progress of COFs photo/electro-catalytic is summarized including design principles, catalytic performance, reaction mechanism. addition, review also presents some challenges prospects application in reduction, laying base fundamental efforts.

Язык: Английский

Процитировано

2
Covalent Organic Frameworks: Opportunities for Rational Materials Design in Cancer Therapy DOI Open Access
Lele Zhou, Qun Guan, Yu‐Bin Dong

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(8)

Опубликована: Ноя. 21, 2023

Nanomedicines are extensively used in cancer therapy. Covalent organic frameworks (COFs) crystalline porous materials with several benefits for therapy, including porosity, design flexibility, functionalizability, and biocompatibility. This review examines the use of COFs therapy from perspective reticular chemistry function-oriented design. First, modification sites functionalization methods discussed, followed by their potential as multifunctional nanoplatforms tumor targeting, imaging, integrating functional components. Finally, some challenges clinical translation presented hope promoting development COF-based anticancer nanomedicines bringing closer to trials.

Язык: Английский

Процитировано

19