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1.
Two novel two-dimensional metal–organic frameworks (2D MOFs), 2D-M 2TCPE (M=Co or Ni, TCPE=1,1,2,2-tetra(4-carboxylphenyl)ethylene), which are composed of staggered (4,4)-grid layers based on paddlewheel-shaped dimers, serve as heterogeneous photocatalysts for efficient reduction of CO 2 to CO. During the visible-light-driven catalysis, these structures undergo in situ exfoliation to form nanosheets, which exhibit excellent stability and improved catalytic activity. The exfoliated 2D-M 2TCPE nanosheets display a high CO evolution rate of 4174 μmol g −1 h −1 and high selectivity of 97.3 % for M=Co and Ni, and thus are superior to most reported MOFs. The performance differences and photocatalytic mechanisms have been studied with theoretical calculations and photoelectric experiments. This study provides new insight for the controllable synthesis of effective crystalline photocatalysts based on structural and morphological coregulation. 相似文献
2.
Metal–organic framework (MOF) NH 2‐Uio‐66(Zr) exhibits photocatalytic activity for CO 2 reduction in the presence of triethanolamine as sacrificial agent under visible‐light irradiation. Photoinduced electron transfer from the excited 2‐aminoterephthalate (ATA) to Zr oxo clusters in NH 2‐Uio‐66(Zr) was for the first time revealed by photoluminescence studies. Generation of Zr III and its involvement in photocatalytic CO 2 reduction was confirmed by ESR analysis. Moreover, NH 2‐Uio‐66(Zr) with mixed ATA and 2,5‐diaminoterephthalate (DTA) ligands was prepared and shown to exhibit higher performance for photocatalytic CO 2 reduction due to its enhanced light adsorption and increased adsorption of CO 2. This study provides a better understanding of photocatalytic CO 2 reduction over MOF‐based photocatalysts and also demonstrates the great potential of using MOFs as highly stable, molecularly tunable, and recyclable photocatalysts in CO 2 reduction. 相似文献
3.
An efficient chemical system for electron generation and transfer is constructed by the integration of an electron mediator ([Co(bpy) 3] 2+; bpy=2,2′‐bipyridine) with semiconductor photocatalysts. The introduction of [Co(bpy) 3] 2+ remarkably enhances the photocatalytic activity of pristine semiconductor photocatalysts for heterogeneous CO 2 conversion; this is attributable to the acceleration of charge separation. Of particular interest is that the excellent photocatalytic activity of heterogeneous catalysts can be developed as a universal photocatalytic CO 2 reduction system. The present findings clearly demonstrate that the integration of an electron mediator with semiconductors is a feasible process for the design and development of efficient photochemical systems for CO 2 conversion. 相似文献
4.
Metal–organic frameworks (MOFs) are crystalline porous materials formed from bi‐ or multipodal organic linkers and transition‐metal nodes. Some MOFs have high structural stability, combined with large flexibility in design and post‐synthetic modification. MOFs can be photoresponsive through light absorption by the organic linker or the metal oxide nodes. Photoexcitation of the light absorbing units in MOFs often generates a ligand‐to‐metal charge‐separation state that can result in photocatalytic activity. In this Review we discuss the advantages and uniqueness that MOFs offer in photocatalysis. We present the best practices to determine photocatalytic activity in MOFs and for the deposition of co‐catalysts. In particular we give examples showing the photocatalytic activity of MOFs in H 2 evolution, CO 2 reduction, photooxygenation, and photoreduction. 相似文献
5.
Single‐site photocatalysts generally display excellent photocatalytic activity and considerably high stability compared with homogeneous catalytic systems. A rational structural design of single‐site photocatalysts with isolated, uniform, and spatially separated active sites in a given solid is of prime importance to achieve high photocatalytic activity. Intense attention has been focused on the design and fabrication of single‐site photocatalysts by using porous materials as a platform. Metal–organic frameworks (MOFs) have great potential in the design and fabrication of single‐site photocatalysts due to their remarkable porosity, ultrahigh surface area, extraordinary tailorability, and significant diversity. MOFs can provide an abundant number of binding sites to anchor active sites, which results in a significant enhancement in photocatalytic performance. In this focus review, the development of single‐site MOF photocatalysts that perform important and challenging chemical redox reactions, such as photocatalytic H 2 production, photocatalytic CO 2 conversion, and organic transformations, is summarized thoroughly. Successful strategies for the construction of single‐site MOF photocatalysts are summarized and major challenges in their practical applications are noted. 相似文献
6.
A series of stable heterometallic Fe 2M cluster-based MOFs ( NNU-31-M , M=Co, Ni, Zn) photocatalysts are presented. They can achieve the overall conversion of CO 2 and H 2O into HCOOH and O 2 without the assistance of additional sacrificial agent and photosensitizer. The heterometallic cluster units and photosensitive ligands excited by visible light generate separated electrons and holes. Then, low-valent metal M accepts electrons to reduce CO 2, and high-valent Fe uses holes to oxidize H 2O. This is the first MOF photocatalyst system to finish artificial photosynthetic full reaction. It is noted that NNU-31-Zn exhibits the highest HCOOH yield of 26.3 μmol g −1 h −1 (selectivity of ca. 100 %). Furthermore, the DFT calculations based on crystal structures demonstrate the photocatalytic reaction mechanism. This work proposes a new strategy for how to design crystalline photocatalyst to realize artificial photosynthetic overall reaction. 相似文献
7.
The integration of photosensitizers with low-cost and non-toxic metal oxides is a promising strategy to design heterogeneous photocatalysts for CO 2 reduction. Herein, p–n heterojunction photocatalysts (T-CoPPcs) consisting of p-type polymeric cobalt phthalocyanines (CoPPcs) as a photosensitizer coupled with n-type TiO 2 nanorods were fabricated through a facile, eco-friendly, one-pot hydrothermal reaction. In this process, CoPPcs were grown on n-type TiO 2 nanorods, whereas protonated titanate nanorods began converting to the highly crystalline anatase phase with small crystals on the TiO 2 surfaces. The introduction of CoPPcs not only improved the solar light utilization but also accelerated the separation and migration of charge carriers via the p–n heterojunction with the strong interfacial contact Ti–O–Co bond. The increases in crystallinity and surface area of TiO 2 nanorods also contributed to the enhanced photoactivities of T-CoPPcs. The CO 2 photoreduction of the synthesized materials was evaluated in CO 2-saturated MeCN/water using [Co(bpy) 3] 2+ as a cocatalyst and triethanolamine as a hole scavenger. The optimized nanocomposite exhibited a remarkable CO generation rate of 4.42 mmol/h/g with a high selectivity of 85.3% and outstanding catalytic stability. The influences of cocatalyst concentration, water content, catalyst loading, and hole scavenger concentration were optimized for efficient CO 2 reduction. The photocatalytic CO 2 conversion efficiency of the present system is found to be higher than that of TiO 2-based materials reported in the literature. We believe that this research into a heterostructural design strategy and photocatalytic system may be an inspiration for the development of photocatalytic CO 2-to-CO conversion. 相似文献
8.
A series of stable heterometallic Fe 2M cluster‐based MOFs ( NNU‐31‐M , M=Co, Ni, Zn) photocatalysts are presented. They can achieve the overall conversion of CO 2 and H 2O into HCOOH and O 2 without the assistance of additional sacrificial agent and photosensitizer. The heterometallic cluster units and photosensitive ligands excited by visible light generate separated electrons and holes. Then, low‐valent metal M accepts electrons to reduce CO 2, and high‐valent Fe uses holes to oxidize H 2O. This is the first MOF photocatalyst system to finish artificial photosynthetic full reaction. It is noted that NNU‐31‐Zn exhibits the highest HCOOH yield of 26.3 μmol g ?1 h ?1 (selectivity of ca. 100 %). Furthermore, the DFT calculations based on crystal structures demonstrate the photocatalytic reaction mechanism. This work proposes a new strategy for how to design crystalline photocatalyst to realize artificial photosynthetic overall reaction. 相似文献
9.
Certain metal complexes are known as high-performance CO 2 reduction photocatalysts driven by visible light. However, most of them rely on rare, precious metals as principal components, and integrating the functions of light absorption and catalysis into a single molecular unit based on abundant metals remains a challenge. Metal-organic frameworks (MOFs), which can be regarded as intermediate compounds between molecules and inorganic solids, are potential platforms for the construction of a simple photocatalytic system composed only of Earth-abundant nontoxic elements. In this work, we report that a tin-based MOF enables the conversion of CO 2 into formic acid with a record high apparent quantum yield (9.8 % at 400 nm) and >99 % selectivity without the need for any additional photosensitizer or catalyst. This work highlights a new MOF with strong potential for photocatalytic CO 2 reduction driven by solar energy. 相似文献
10.
The increasing pollution and human demand for a cleaner environment have made achieving the environmental sustainability a current research focus. As a “green” technology, semiconductor photocatalysis is of great significance to the environmental purification. Benefiting from the unique anisotropic crystal structure and electronic properties, layered photocatalytic nanomaterials show great potential for efficient photocatalytic environmental treatment. This review comprehensively summarizes the recent progress on layered photocatalytic nanomaterials for oxidation or reduction of pollutants in water and air along with the basic understanding of related mechanisms and developments in this field. First, the existing diversified layered photocatalysts are classified, and their different synthesis and modification strategies are discussed in detail to provide a comprehensive view of the material design that affects their photocatalytic performance. Subsequently, the extensive applications of the above-mentioned layered photocatalytic nanomaterials in environmental fields are systematically summarized, including photooxidation of water and air pollutants, and photoreduction of heavy metal pollutants, NO 3?, BrO 3? and CO 2. Finally, based on the current research achievements in layered photocatalysts for environmental remediation, the future development direction and challenges are proposed. 相似文献
11.
Modular optimization of metal–organic frameworks (MOFs) was realized by incorporation of coordinatively unsaturated single atoms in a MOF matrix. The newly developed MOF can selectively capture and photoreduce CO 2 with high efficiency under visible‐light irradiation. Mechanistic investigation reveals that the presence of single Co atoms in the MOF can greatly boost the electron–hole separation efficiency in porphyrin units. Directional migration of photogenerated excitons from porphyrin to catalytic Co centers was witnessed, thereby achieving supply of long‐lived electrons for the reduction of CO 2 molecules adsorbed on Co centers. As a direct result, porphyrin MOF comprising atomically dispersed catalytic centers exhibits significantly enhanced photocatalytic conversion of CO 2, which is equivalent to a 3.13‐fold improvement in CO evolution rate (200.6 μmol g ?1 h ?1) and a 5.93‐fold enhancement in CH 4 generation rate (36.67 μmol g ?1 h ?1) compared to the parent MOF. 相似文献
12.
Photocatalytic oxidation of sulfide into sulfoxide has attracted extensive attention as an environmentally friendly strategy for chemical transformations or toxic chemicals degradation. Herein, we construct a series of In 2S 3/NU-1000 heterojunction photocatalysts, which can efficiently catalyze the oxidation of sulfides to form sulfoxides as the sole product under LED lamp (full-spectrum) illumination in air at room temperature. Especially, the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), can also be photocatalytically oxidized with In 2S 3/NU-1000 to afford nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) selectively and effectively. In contrast, individual NU-1000 and In 2S 3 show very low catalytic activity on this reaction. The significantly improved photocatalytic activity is ascribed to the constructing of an efficient Z-scheme photocatalysts In 2S 3/NU-1000, which exhibits the enhancement of light harvesting, the promotion of photogenerated electron-hole separation, and the retention of high porosity of the parent MOF. Moreover, mechanism studies in photocatalytic oxidation reveal that the superoxide radical ( .O 2−) and singlet oxygen ( 1O 2) are the main oxidative species in the oxidation system. This work exploits the opportunities for the construction of porous Z-scheme photocatalysts based on the photoactive MOFs materials and inorganic semiconductors for promoting catalytic organic transformations. More importantly, it provides a route to the rational design of efficient photocatalysts for the detoxification of mustard gas. 相似文献
13.
Photoconversion of CO 2 and H 2O into ethanol is an ideal strategy to achieve carbon neutrality. However, the production of ethanol with high activity and selectivity is challenging owing to the less efficient reduction half-reaction involving multi-step proton-coupled electron transfer (PCET), a slow C−C coupling process, and sluggish water oxidation half-reaction. Herein, a two-dimensional/two-dimensional (2D/2D) S-scheme heterojunction consisting of black phosphorus and Bi 2WO 6 (BP/BWO) was constructed for photocatalytic CO 2 reduction coupling with benzylamine (BA) oxidation. The as-prepared BP/BWO catalyst exhibits a superior photocatalytic performance toward CO 2 reduction, with a yield of 61.3 μmol g −1 h −1 for ethanol (selectivity of 91 %).In situ spectroscopic studies and theoretical calculations reveal that S-scheme heterojunction can effectively promote photogenerated carrier separation via the Bi−O−P bridge to accelerate the PCET process. Meanwhile, electron-rich BP acts as the active site and plays a vital role in the process of C−C coupling. In addition, the substitution of BA oxidation for H 2O oxidation can further enhance the photocatalytic performance of CO 2 reduction to C 2H 5OH. This work opens a new horizon for exploring novel heterogeneous photocatalysts in CO 2 photoconversion to C 2H 5OH based on cooperative photoredox systems. 相似文献
14.
Metal-organic frameworks(MOFs) as a type of crystalline heterogeneous catalysts have shown potential application in photocatalytic CO 2 reduction.However,MOF catalysts with high efficiency and selectivity are still in pursuit.Herein,by a bimetallic strategy,the catalytic performance of a Co-MOF for photocatalytic CO 2 reduction was enhanced.Specifically,the Co-MOF based on 4,5-dicarboxylic acid(H 3 IDC) and4,4’-bipydine(4,4’-bpy) can catalyze CO 2 reductio... 相似文献
15.
Photocatalytic conversion of CO 2 is of great interest but it often suffers sluggish oxidation half reaction and undesired by-products. Here, we report for the first the simultaneous co-photocatalytic CO 2 reduction and ethanol oxidation towards one identical value-added CH 3CHO product on a rubidium and potassium co-modified carbon nitride (CN-KRb). The CN-KRb offers a record photocatalytic activity of 1212.3 μmol h −1g −1 with a high selectivity of 93.3 % for CH 3CHO production, outperforming all the state-of-art CO 2 photocatalysts. It is disclosed that the introduced Rb boosts the *OHCCHO fromation and facilitates the CH 3CHO desorption, while K promotes ethanol adsorption and activation. Moreover, the H + stemming from ethanol oxidation is confirmed to participate in the CO 2 reduction process, endowing near ideal overall atomic economy. This work provides a new strategy for effective use of the photoexcited electron and hole for high selective and sustainable conversion of CO 2 paired with oxidation reaction into identical product. 相似文献
16.
Artificial photosynthesis—reduction of CO 2 into chemicals and fuels with water oxidation in the presence of sunlight as the energy source—mimics natural photosynthesis in green plants, and is considered to have a significant part to play in future energy supply and protection of our environment. The high quantum efficiency and easy manipulation of heterogeneous molecular photosystems based on metal complexes enables them to act as promising platforms to achieve efficient conversion of solar energy. This Review describes recent developments in the heterogenization of such photocatalysts. The latest state‐of‐the‐art approaches to overcome the drawbacks of low durability and inconvenient practical application in homogeneous molecular systems are presented. The coupling of photocatalytic CO 2 reduction with water oxidation through molecular devices to mimic natural photosynthesis is also discussed. 相似文献
17.
Solid solution-oxide heterostructures combine the advantages of solid solution and heterojunction materials to improve electronic structure and optical properties by metal doping, and enhance charge separation and transfer in semiconductor photocatalysts by creating a built-in electric field. Nevertheless, the effective design and synthesis of these materials remains a significant challenge. Here, we develop a generally applicable strategy that leverages the transformable properties of metal–organic frameworks (MOFs) to prepare solid solution-oxide heterojunctions with controllable structural and chemical compositions. The process consists of three main steps. First, MOFs with different topological structures and metal centers are transformed, accompanied by pre-nucleation of a metal oxide. Second, solid solution is prepared through calcination of the transformed MOFs. Finally, a heterojunction is formed by combining solid solution with another metal oxide group through endogenous overflow. DFT calculations and study on carrier dynamics show that the structure of the material effectively prevents electrons from returning to the bulk phase, exhibiting superior photocatalytic reduction performance of CO 2. This study is expected to promote the controllable synthesis and research of MOF-derived heterojunctions. 相似文献
18.
Photoactive metal–organic frameworks (MOFs) have proven to be a promising porous material in the field of catalysis. Controllable integration of these MOFs with inorganic semiconductor materials may endow new multifunctional hybrid materials with preferable photocatalytic properties. In this research, NH2-MIL-125(Ti) nanoplates modified Bi2WO6 microspheres was prepared via a simple solvothermal method. The photocatalytic behaviors of the acquired catalysts was evaluated via the degradation of tetracycline hydrochloride (TC) under visible light. The experimental results showed that NH2-MIL-125(Ti)/Bi2WO6 composites display higher photocatalytic activity than that of single Bi2WO6, and the ideal incorporation amount of NH2-MIL-125(Ti) was around 5 wt%. The steady state fluorescence spectrum, transient photocurrents and electrochemical impedance spectroscopy verified that the introduction of NH2-MIL-125(Ti) could accelerate the separation and transfer of photogenerated carriers and thus improve the photocatalytic activity of Bi2WO6. The photocatalytic mechanism was explored in detail. This work extends the knowledge of integrating MOFs with traditional photocatalysts to form new composite materials in the area of environmental purification. 相似文献
19.
Metal-organic framework nanosheets (MOF NNs) offer potential opportunities for many applications,but an efficient strategy for the scalable preparation of few-layered two-dimensional (2D) MOF NNs are still a major challenge.Herein,we present an efficient top-down method for the synthesis of the Ni-BDC(Ni 2(OH) 2(1,4-BDC);1,4-BDC=1,4-benzenedicarboxylate) nanosheets utilizing a novel thermal expansionquench method of the flowerlike bulky MOFs in liquid N 2.The obtain... 相似文献
20.
传统化石能源燃烧产生CO 2引起的地球变暖和能源短缺已经成为一个严重的全球性问题. 利用太阳光和光催化材料将CO 2还原为碳氢燃料, 不仅可以减少空气中CO 2浓度, 降低温室效应的影响, 还可以提供碳氢燃料, 缓解能源短缺问题, 因此日益受到各国科学家的高度关注. 本文综述了光催化还原CO 2为碳氢燃料的研究进展, 介绍了光催化还原CO 2的反应机理, 并对现阶段报道的光催化还原CO 2材料体系进行了整理和分类, 包括TiO 2光催化材料, ABO 3型钙钛矿光催化材料, 尖晶石型光催化材料, 掺杂型光催化材料, 复合光催化材料, V、W、Ge、Ga基光催化材料及石墨烯基光催化材料. 评述了各种材料体系的特点及光催化性能的一些影响因素. 最后对光催化还原CO 2的研究前景进行了展望. 相似文献
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