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1.
A Methylthio‐Functionalized‐MOF Photocatalyst with High Performance for Visible‐Light‐Driven H2 Evolution
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Hui Chen Xian‐Bao Bu Yi‐Xuan Gao Hui Gao Prof. Yang Tian Prof. Gui‐Sheng Li Prof. Guo Wang Prof. Sheng‐Li Cao Prof. Chong‐Qing Wan Prof. Guo‐Cong Guo 《Angewandte Chemie (International ed. in English)》2018,57(31):9864-9869
Recently, the emergence of photoactive metal–organic frameworks (MOFs) has given great prospects for their applications as photocatalytic materials in visible‐light‐driven hydrogen evolution. Herein, a highly photoactive visible‐light‐driven material for H2 evolution was prepared by introducing methylthio terephthalate into a MOF lattice via solvent‐assisted ligand‐exchange method. Accordingly, a first methylthio‐functionalized porous MOF decorated with Pt co‐catalyst for efficient photocatalytic H2 evolution was achieved, which exhibited a high quantum yield (8.90 %) at 420 nm by use sacrificial triethanolamine. This hybrid material exhibited perfect H2 production rate as high as 3814.0 μmol g?1 h?1, which even is one order of magnitude higher than that of the state‐of‐the‐art Pt/MOF photocatalyst derived from aminoterephthalate. 相似文献
2.
A Noble‐Metal‐Free Nickel(II) Polypyridyl Catalyst for Visible‐Light‐Driven Hydrogen Production from Water
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Dr. Yong‐Jun Yuan Dr. Hong‐Wei Lu Ji‐Ren Tu Dr. Yong Fang Dr. Zhen‐Tao Yu Dr. Xiao‐Xing Fan Prof. Zhi‐Gang Zou 《Chemphyschem》2015,16(14):2925-2930
The complex [Ni(bpy)3]2+ (bpy=2,2′‐bipyridine) is an active catalyst for visible‐light‐driven H2 production from water when employed with [Ir(dfppy)2(Hdcbpy)] [dfppy=2‐(3,4‐difluorophenyl)pyridine, Hdcbpy=4‐carboxy‐2,2′‐bipyridine‐4′‐carboxylate] as the photosensitizer and triethanolamine as the sacrificial electron donor. The highest turnover number of 520 with respect to the nickel(II) catalyst is obtained in a 8:2 acetonitrile/water solution at pH 9. The H2‐evolution system is more stable after the addition of an extra free bpy ligand, owing to faster catalyst regeneration. The photocatalytic results demonstrate that the nickel(II) polypyridyl catalyst can act as a more effective catalyst than the commonly utilized [Co(bpy)3]2+. This study may offer a new paradigm for constructing simple and noble‐metal‐free catalysts for photocatalytic hydrogen production. 相似文献
3.
Preparation of disk‐like Pt/CeO2‐p‐TiO2 catalyst derived from MIL‐125(Ti) for excellent catalytic performance
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Shenhao Yuan Yan Gao Jiehua Bao Yiwei Zhang Wenxia Chen Jiasheng Fang Yuming Zhou Yanyun Wang Wenyu Zhu 《应用有机金属化学》2018,32(7)
A feasible strategy is reported for the synthesis of a disk‐like Pt/CeO2‐p‐TiO2 catalyst derived from the titanium‐based metal–organic framework (MOF) MIL‐125(Ti) through a few valid steps. To verify the successful synthesis and structural features of the Pt/CeO2‐p‐TiO2 catalyst, as‐prepared samples were characterized using several techniques. The characterizations demonstrated that MOF‐derived porous TiO2 was appropriate for application as a support owing to its moderate surface area (101 m2 g?1) and suitable pore size (6 nm). Moreover, to study the effect of calcination temperature on the catalytic performance, the obtained catalyst was calcined at various temperatures. It was found that Pt/CeO2‐p‐TiO2 calcined at 550 °C exhibited the highest catalytic performance, evaluated by means of the reduction of 4‐nitrophenol monitored by UV–visible spectra. Furthermore, this catalyst showed good reusability with a conversion of 94% even after six cycles. Finally, a possible reaction mechanism was proposed to explain the reduction of 4‐nitrophenol to 4‐aminophenol over the Pt/CeO2‐p‐TiO2 catalyst. 相似文献
4.
An Efficient,Visible‐Light‐Driven,Hydrogen Evolution Catalyst NiS/ZnxCd1−xS Nanocrystal Derived from a Metal–Organic Framework
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Dr. Xiuxia Zhao Jianrui Feng Jing Liu Prof. Wei Shi Prof. Guangming Yang Prof. Gui‐Chang Wang Prof. Peng Cheng 《Angewandte Chemie (International ed. in English)》2018,57(31):9790-9794
Photocatalytic water splitting for hydrogen production using sustainable sunlight is a promising alternative to industrial hydrogen production. However, the scarcity of highly active, recyclable, inexpensive photocatalysts impedes the development of photocatalytic hydrogen evolution reaction (HER) schemes. Herein, a metal–organic framework (MOF)‐template strategy was developed to prepare non‐noble metal co‐catalyst/solid solution heterojunction NiS/ZnxCd1?xS with superior photocatalytic HER activity. By adjusting the doping metal concentration in MOFs, the chemical compositions and band gaps of the heterojunctions can be fine‐tuned, and the light absorption capacity and photocatalytic activity were further optimized. NiS/Zn0.5Cd0.5S exhibits an optimal HER rate of 16.78 mmol g?1 h?1 and high stability and recyclability under visible‐light irradiation (λ>420 nm). Detailed characterizations and in‐depth DFT calculations reveal the relationship between the heterojunction and photocatalytic activity and confirm the importance of NiS in accelerating the water dissociation kinetics, which is a crucial factor for photocatalytic HER. 相似文献
5.
Density Functional Theory Study of Hydrogen Adsorption in a Ti‐Decorated Mg‐Based Metal–Organic Framework‐74
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Pitphichaya Suksaengrat Prof. Dr. Vittaya Amornkitbamrung Dr. Pornjuk Srepusharawoot Prof. Dr. Rajeev Ahuja 《Chemphyschem》2016,17(6):879-884
The Ti‐binding energy and hydrogen adsorption energy of a Ti‐decorated Mg‐based metal–organic framework‐74 (Mg‐MOF‐74) were evaluated by using first‐principles calculations. Our results revealed that only three Ti adsorption sites were found to be stable. The adsorption site near the metal oxide unit is the most stable. To investigate the hydrogen‐adsorption properties of Ti‐functionalized Mg‐MOF‐74, the hydrogen‐binding energy was determined. For the most stable Ti adsorption site, we found that the hydrogen adsorption energy ranged from 0.26 to 0.48 eV H2?1. This is within the desirable range for practical hydrogen‐storage applications. Moreover, the hydrogen capacity was determined by using ab initio molecular dynamics simulations. Our results revealed that the hydrogen uptake by Ti‐decorated Mg‐MOF‐74 at temperatures of 77, 150, and 298 K and ambient pressure were 1.81, 1.74, and 1.29 H2 wt %, respectively. 相似文献
6.
Teng Liu Peng Li Na Yao Gongzhen Cheng Shengli Chen Wei Luo Yadong Yin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(14):4727-4732
Although electrocatalysts based on transition metal phosphides (TMPs) with cationic/anionic doping have been widely studied for hydrogen evolution reaction (HER), the origin of performance enhancement still remains elusive mainly due to the random dispersion of dopants. Herein, we report a controllable partial phosphorization strategy to generate CoP species within the Co‐based metal‐organic framework (Co‐MOF). Density functional theory calculations and experimental results reveal that the electron transfer from CoP to Co‐MOF through N‐P/N‐Co bonds could lead to the optimized adsorption energy of H2O (ΔG ) and hydrogen (ΔGH*), which, together with the unique porous structure of Co‐MOF, contributes to the remarkable HER performance with an overpotential of 49 mV at a current density of 10 mA cm?2 in 1 m phosphate buffer solution (PBS, pH 7.0). The excellent catalytic performance exceeds almost all the documented TMP‐based and non‐noble‐metal‐based electrocatalysts. In addition, the CoP/Co‐MOF hybrid also displays Pt‐like performance in 0.5 m H2SO4 and 1 m KOH, with the overpotentials of 27 and 34 mV, respectively, at a current density of 10 mA cm?2. 相似文献
7.
Pd Nanocubes@ZIF‐8: Integration of Plasmon‐Driven Photothermal Conversion with a Metal–Organic Framework for Efficient and Selective Catalysis
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Qihao Yang Prof. Dr. Qiang Xu Prof. Dr. Shu‐Hong Yu Prof. Dr. Hai‐Long Jiang 《Angewandte Chemie (International ed. in English)》2016,55(11):3685-3689
Composite nanomaterials usually possess synergetic properties resulting from the respective components and can be used for a wide range of applications. In this work, a Pd nanocubes@ZIF‐8 composite material has been rationally fabricated by encapsulation of the Pd nanocubes in ZIF‐8, a common metal–organic framework (MOF). This composite was used for the efficient and selective catalytic hydrogenation of olefins at room temperature under 1 atm H2 and light irradiation, and benefits from plasmonic photothermal effects of the Pd nanocube cores while the ZIF‐8 shell plays multiple roles; it accelerates the reaction by H2 enrichment, acts as a “molecular sieve” for olefins with specific sizes, and stabilizes the Pd cores. Remarkably, the catalytic efficiency of a reaction under 60 mW cm?2 full‐spectrum or 100 mW cm?2 visible‐light irradiation at room temperature turned out to be comparable to that of a process driven by heating at 50 °C. Furthermore, the catalyst remained stable and could be easily recycled. To the best of our knowledge, this work represents the first combination of the photothermal effects of metal nanocrystals with the favorable properties of MOFs for efficient and selective catalysis. 相似文献
8.
Jun‐Hua Wei Jing‐Wei Yi Min‐Le Han Bo Li Shan Liu Ya‐Pan Wu Lu‐Fang Ma Dong‐Sheng Li 《化学:亚洲杂志》2019,14(20):3694-3701
Effective detection of organic/inorganic pollutants, such as antibiotics, nitro‐compounds, excessive Fe3+ and MnO4?, is crucial for human health and environmental protection. Here, a new terbium(III)–organic framework, namely [Tb(TATAB)(H2O)]?2H2O ( Tb‐MOF , H3TATAB=4,4′,4′′‐s‐triazine‐1,3,5‐triyltri‐m‐aminobenzoic acid), was assembled and characterized. The Tb‐MOF exhibits a water‐stable 3D bnn framework. Due to the existence of competitive absorption, Tb‐MOF has a high selectivity for detecting Fe3+, MnO4?, 4‐nirophenol and nitroimidazole (ronidazole, metronidazole, dimetridazole, ornidazole) in aqueous through luminescent quenching. The results suggest that Tb‐MOF is a simple and reliable reagent with multiple sensor responses in practical applications. To the best of our knowledge, this work represents the first TbIII‐based MOF as an efficient fluorescent sensor for detecting metal ions, inorganic anions, nitro‐compounds, and antibiotics simultaneously. 相似文献
9.
Proton Transport in a Highly Conductive Porous Zirconium‐Based Metal–Organic Framework: Molecular Insight
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Dr. Daiane Damasceno Borges Dr. Sabine Devautour‐Vinot Dr. Hervé Jobic Dr. Jacques Ollivier Dr. Farid Nouar Dr. Rocio Semino Dr. Thomas Devic Dr. Christian Serre Prof. Francesco Paesani Prof. Guillaume Maurin 《Angewandte Chemie (International ed. in English)》2016,55(12):3919-3924
The water stable UiO‐66(Zr)‐(CO2H)2 MOF exhibits a superprotonic conductivity of 2.3×10?3 S cm?1 at 90 °C and 95 % relative humidity. Quasi‐elastic neutron scattering measurements combined with aMS‐EVB3 molecular dynamics simulations were able to probe individually the dynamics of both confined protons and water molecules and to further reveal that the proton transport is assisted by the formation of a hydrogen‐bonded water network that spans from the tetrahedral to the octahedral cages of this MOF. This is the first joint experimental/modeling study that unambiguously elucidates the proton‐conduction mechanism at the molecular level in a highly conductive MOF. 相似文献
10.
Feiyan Zhang Yuming Dong Pingping Jiang Guangli Wang Na Zhao Huizhen Zhang Dandan Li Jinze Lyu Yan Wang Ji Li Yongfa Zhu 《化学:亚洲杂志》2019,14(23):4193-4200
Photodeposition has been widely used as a mild and efficient synthetic method to deposit co‐catalysts. It is also worth studying how to synthesize non‐noble metal photocatalysts with uniform dispersion. Different synthetic conditions in photodeposition have a certain influence on particle size distribution and photocatalytic activity. Therefore, we designed experiments to prepare the inexpensive composite photocatalyst Ni(OH)2/g‐C3N4 by photodeposition. The Ni(OH)2 co‐catalysts disperse uniformly with particle sizes of about 10 nm. The photocatalytic hydrogen production rate of Ni(OH)2/g‐C3N4 reached about 19 mmol g?1 h?1, with the Ni(OH)2 deposition amount about 1.57 %. During 16 h stability testing, the rate of hydrogen production did not decrease significantly. The composite catalyst also revealed a good hydrogen production performance under sunlight. The Ni(OH)2 co‐catalyst enhanced the separation ability of photogenerated carriers, which was proved by surface photovoltage and fluorescence analysis. 相似文献
11.
The synthesis of a metal–organic framework (MOF) named IITI‐1 is reported by employing an H2L linker with Cu(NO3)2?3 H2O in a mixed solvent system of N,N‐dimethyl formamide (DMF) and H2O. Further, in order to explore the energy storage application of IITI‐1 , a IITI‐1/CNT hybrid was prepared by a simple ultrasonication technique. Incorporation of a carbon nanotube (CNT) in the layered IITI‐1 MOF gave rise to enhanced electrolyte accessibility along with improved electrochemical storage capacity. The electrochemical investigations reveal a high specific capacitance (380 F g?1 at 1.6 A g?1) with a good rate performance for IITI‐1/CNT . The IITI‐1 MOF and the IITI‐1/CNT composite were characterized by PXRD, BET, SEM, and TEM techniques. Moreover, IITI‐1 MOF was also confirmed by single‐crystal XRD analysis. 相似文献
12.
《应用有机金属化学》2017,31(12)
A Zr‐based metal–organic framework with bipyridine units (UiO‐67) has been utilized for the immobilization of catalytically active iron species via a post‐synthetic metalation method. UiO‐67 bipyridine MOF was synthesized through a simple solvothermal method and was shown to have a UiO‐type structure. Post‐synthetic metalation of UiO‐67 MOF was performed for the immobilization of the catalytically active FeCl3. FT‐IR and EDX element map suggested that FeCl3 is coordinately bonded to the UiO‐67 bipyridine framework. The synthesized UiO‐67‐FeCl3 catalyst was used for the aerobic oxidation of alcohols and benzylic compounds in the presence of molecular oxygen. In addition, the UiO‐67‐FeCl3 catalyst can be reused as a solid heterogeneous catalyst without compromising its activity and selectivity. 相似文献
13.
Yong Dou Lu Yang Lan Qin Yunhui Dong Zhen Zhou Daopeng Zhang Suna Wang 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(6):616-624
The solar photocatalysis of water splitting represents a significant branch of enzymatic simulation by efficient chemical conversion and the generation of hydrogen as green energy provides a feasible way for the replacement of fossil fuels to solve energy and environmental issues. We report herein the self‐assembly of a CoII‐based metal–organic framework (MOF) constructed from 4,4′,4′′,4′′′‐(ethene‐1,1,2,2‐tetrayl)tetrabenzoic acid [or tetrakis(4‐carboxyphenyl)ethylene, H4TCPE] and 4,4′‐bipyridyl (bpy) as four‐point‐ and two‐point‐connected nodes, respectively. This material, namely, poly[(μ‐4,4′‐bipyridyl)[μ8‐4,4′,4′′,4′′′‐(ethene‐1,1,2,2‐tetrayl)tetrabenzoato]cobalt(II)], [Co(C30H16O8)(C10H8N2)]n, crystallized as dark‐red block‐shaped crystals with high crystallinity and was fully characterized by single‐crystal X‐ray diffraction, PXRD, IR, solid‐state UV–Vis and cyclic voltammetry (CV) measurements. The redox‐active CoII atoms in the structure could be used as the catalytic sites for hydrogen production via water splitting. The application of this new MOF as a heterogeneous catalyst for light‐driven H2 production has been explored in a three‐component system with fluorescein as photosensitizer and trimethylamine as the sacrificial electron donor, and the initial volume of H2 production is about 360 µmol after 12 h irradiation. 相似文献
14.
Formation of Ultrathin,Continuous Metal–Organic Framework Membranes on Flexible Polymer Substrates
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Dr. Jingwei Hou Putu D. Sutrisna Prof. Yatao Zhang Prof. Vicki Chen 《Angewandte Chemie (International ed. in English)》2016,55(12):3947-3951
Metal–organic framework (MOF) materials have an enormous potential in separation applications, but to realize their potential as semipermeable membranes they need to be assembled into thin continuous macroscopic films for fabrication into devices. By using a facile immersion technique, we prepared ultrathin, continuous zeolitic imidazolate framework (ZIF‐8) membranes on titania‐functionalized porous polymeric supports. The coherent ZIF‐8 layer was surprisingly flexible and adhered well to the support, and the composite membrane could sustain bending and elongation. The membranes exhibited molecular sieving behavior, close to the theoretical permeability of ZIF‐8, with hydrogen permeance up to 201×10?7 mol m?2 s?1 Pa?1 and an ideal H2/CO2 selectivity of 7:1. This approach offers significant opportunities to exploit the unique properties of MOFs in the fabrication of separation and sensing devices. 相似文献
15.
Quan Zuo Tingting Liu Chuanshuang Chen Yi Ji Xueqing Gong Yiyong Mai Yongfeng Zhou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(30):10304-10309
A surfactant‐stabilized coordination strategy is used to make two‐dimensional (2D) single‐atom catalysts (SACs) with an ultrahigh Pt loading of 12.0 wt %, by assembly of pre‐formed single Pt atom coordinated porphyrin precursors into free‐standing metal–organic framework (MOF) nanosheets with an ultrathin thickness of 2.4±0.9 nm. This is the first example of 2D MOF‐based SACs. Remarkably, the 2D SACs exhibit a record‐high photocatalytic H2 evolution rate of 11 320 μmol g?1 h?1 via water splitting under visible light irradiation (λ>420 nm) compared with those of reported MOF‐based photocatalysts. Moreover, the MOF nanosheets can be readily drop‐casted onto solid substrates, forming thin films while still retaining their photocatalytic activity, which is highly desirable for practical solar H2 production. 相似文献
16.
Jia Wang Tianchao You Teng Wang Qikui Liu Jianping Ma Guoxia Jin 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(6):806-811
The adsorption behaviour of the CdII–MOF {[Cd(L)2(ClO4)2]·H2O ( 1 ), where L is 4‐amino‐3,5‐bis[3‐(pyridin‐4‐yl)phenyl]‐1,2,4‐triazole, for butan‐2‐one was investigated in a single‐crystal‐to‐single‐crystal (SCSC) fashion. A new host–guest system that encapsulated butan‐2‐one molecules, namely poly[[bis{μ3‐4‐amino‐3,5‐bis[3‐(pyridin‐4‐yl)phenyl]‐1,2,4‐triazole}cadmium(II)] bis(perchlorate) butanone sesquisolvate], {[Cd(C24H18N6)2](ClO4)2·1.5C4H8O}n, denoted C4H8O@Cd‐MOF ( 2 ), was obtained via an SCSC transformation. MOF 2 crystallizes in the tetragonal space group P43212. The specific binding sites for butan‐2‐one in the host were determined by single‐crystal X‐ray diffraction studies. N—H…O and C—H…O hydrogen‐bonding interactions and C—H…π interactions between the framework, ClO4? anions and guest molecules co‐operatively bind 1.5 butan‐2‐one molecules within the channels. The adsorption behaviour was further evidenced by 1H NMR, IR, TGA and powder X‐ray diffraction experiments, which are consistent with the single‐crystal X‐ray analysis. A 1H NMR experiment demonstrates that the supramolecular interactions between the framework, ClO4? anions and guest molecules in MOF 2 lead to a high butan‐2‐one uptake in the channel. 相似文献
17.
Clean Donor Oxidation Enhances the H2 Evolution Activity of a Carbon Quantum Dot–Molecular Catalyst Photosystem
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Benjamin C. M. Martindale Evelyne Joliat Dr. Cyril Bachmann Prof. Dr. Roger Alberto Dr. Erwin Reisner 《Angewandte Chemie (International ed. in English)》2016,55(32):9402-9406
Carbon quantum dots (CQDs) are new‐generation light absorbers for photocatalytic H2 evolution in aqueous solution, but the performance of CQD‐molecular catalyst systems is currently limited by the decomposition of the molecular component. Clean oxidation of the electron donor by donor recycling prevents the formation of destructive radical species and non‐innocent oxidation products. This approach allowed a CQD‐molecular nickel bis(diphosphine) photocatalyst system to reach a benchmark lifetime of more than 5 days and a record turnover number of 1094±61 molH2 (molNi)?1 for a defined synthetic molecular nickel catalyst in purely aqueous solution under AM1.5G solar irradiation. 相似文献
18.
Sequential Transformation of Zirconium(IV)‐MOFs into Heterobimetallic MOFs Bearing Magnetic Anisotropic Cobalt(II) Centers
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Dr. Shuai Yuan Dr. Jun‐Sheng Qin Jian Su Dr. Bao Li Jialuo Li Wenmiao Chen Hannah F. Drake Dr. Peng Zhang Dr. Daqiang Yuan Prof. Dr. Jinglin Zuo Prof. Dr. Hong‐Cai Zhou 《Angewandte Chemie (International ed. in English)》2018,57(38):12578-12583
Heterometallic metal–organic frameworks (MOFs) allow the precise placement of various metals at atomic precision within a porous framework. This new level of control by MOFs promises fascinating advances in basic science and application. However, the rational design and synthesis of heterometallic MOFs remains a challenge due to the complexity of the heterometallic systems. Herein, we show that bimetallic MOFs with MX2(INA)4 moieties (INA=isonicotinate; M=Co2+ or Fe2+; X=OH?, Cl?, Br?, I?, NCS?, or NCSe?) can be generated by the sequential modification of a Zr‐based MOF. This multi‐step modification not only replaced the linear organic linker with a square planar MX2(INA)4 unit, but also altered the symmetry, unit cell, and topology of the parent structure. Single‐crystal to single‐crystal transformation is realized so that snapshots for transition process were captured by successive single‐crystal X‐ray diffraction. Furthermore, the installation of Co(NCS)2(INA)4 endows field‐induced slow magnetic relaxation property to the diamagnetic Zr‐MOF. 相似文献
19.
Efficient Visible‐Light‐Driven Carbon Dioxide Reduction by a Single‐Atom Implanted Metal–Organic Framework
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Dr. Huabin Zhang Dr. Jing Wei Dr. Juncai Dong Dr. Guigao Liu Li Shi Dr. Pengfei An Dr. Guixia Zhao Dr. Jintao Kong Dr. Xiaojun Wang Dr. Xianguang Meng Prof. Jing Zhang Prof. Jinhua Ye 《Angewandte Chemie (International ed. in English)》2016,55(46):14310-14314
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 CO2 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 CO2 molecules adsorbed on Co centers. As a direct result, porphyrin MOF comprising atomically dispersed catalytic centers exhibits significantly enhanced photocatalytic conversion of CO2, 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 CH4 generation rate (36.67 μmol g?1 h?1) compared to the parent MOF. 相似文献
20.
Sabine Schuster Prof. Dr. Elias Klemm Prof. Dr. Matthias Bauer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(49):15831-15837
The metal–organic framework (MOF) [Pd(2‐pymo)2]n (2‐pymo=2‐pyrimidinolate) was used as catalyst in the hydrogenation of 1‐octene. During catalytic hydrogenation, the changes at the metal nodes and linkers of the MOF were investigated by in situ X‐ray absorption spectroscopy (XAS) and IR spectroscopy. With the help of extended X‐ray absorption fine structure and X‐ray absorption near edge structure data, Quick‐XAS, and IR spectroscopy, detailed insights into the catalytic relevance of Pd2+/Pd0 in the hydrogenation of 1‐octene could be achieved. Shortly after exposure of the catalyst to H2 and simultaneously with the hydrogenation of 1‐octene, the aromatic rings of the linker molecules are hydrogenated rapidly. Up to this point, the MOF structure remained intact. After completion of linker hydrogenation, the linkers were also protonated. When half of the linker molecules were protonated, the onset of reduction of the Pd2+ centers to Pd0 was observed and the hydrogenation activity decreased, followed by fast reduction of the palladium centers and collapse of the MOF structure. Major fractions of Pd0 are only observed when the hydrogenation of 1‐octene is almost finished. Consequently, the Pd2+ nodes of the MOF [Pd(2‐pymo)2]n are identified as active centers in the hydrogenation of 1‐octene. 相似文献