DALTON TRANSACTIONS
·
2023
·Vol. 52
·期 21
·7119-7128
·
IF 4
Zhengguo Zhang,Hongxiao Lv,Kun Yang,Xiutang Zhang
Developing materials with excellent properties has become the norm in the field of basic research, prompting us to explore highly robust hybrid materials based on electron-rich POMs and electron-deficient MOFs. Herein, a θ-[Mo8O26]4−-based hybrid material of [Cu2(BPPP)2]{θ-[Mo8O26]} (NUC-62) with excellent physicochemical stability was self-assembled under acidic solvothermal conditions from Na2MoO4 and CuCl2 in the presence of a designed chelated ligand of 1,3-bis(3-(2-pyridyl)pyrazol-1-yl)propane (BPPP), which has sufficient coordination sites, spatial self-regulation and great deformation ability. In NUC-62, each of two tetra-coordinated CuII ions and two BPPP are unified into one dinuclear unit serving as the cation, which is interactively linked to θ-[Mo8O26]4− anions via rich hydrogen bonds of C–H⋯O. Because of the unsaturated Lewis acidic CuII sites, NUC-62 exhibits high catalytic performance on the cycloaddition reactions of CO2 with epoxides under mild conditions with a high turnover number and turnover frequency. Furthermore, NUC-62, as a recyclable heterogeneous catalyst, shows high catalytic activity for the esterification of aromatic acid under refluxing, which is much better than the inorganic acid catalyst of H2SO4 in terms of turnover number and turnover frequency. Moreover, because of open metal sites and rich terminal oxygen atoms, NUC-62 shows high catalytic activity for Knoevenagel condensation reactions of aldehydes and malononitrile. Hence, this study lays the groundwork for constructing heterometallic cluster-based microporous MOFs with excellent Lewis acidic catalysis and chemical stability. Therefore, this study lays a foundation for the construction of functional polyoxometalate complexes.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2021
·
IF 19.503
Guangyao Zhai,Yuanyuan Liu,Yuyin Mao,Honggang Zhang,Lingtong Lin,Yujie Li,Zeyan Wang,Hefeng Cheng,Peng Wang,Zhaoke Zheng,Ying Dai,Baibiao Huang
CO 2 cycloaddition reaction from propylene oxide and CO 2 to cyclic carbonates is a desirable process to become carbon neutral. Photo energy can decrease the temperature and pressure needed for this reaction according to our previous results. However, the relationship between Lewis acidity and the photophysical process needs to be clarified and optimized. Hence, in this work, Zn is introduced into UiO-bpydc via the coordination of Zn with the bipyridyl group in bpydc. It is found that the introduction of Zn not only effectively activate propylene oxide, but also promote ligand to metal charge transfer (LMCT) process, which ultimately is beneficial for CO 2 activation. However, Ce plays a negative effect under light irradiation. namely, the presence of Ce facilitates the energy transfer process rather than the LMCT process.
研究领域:
材料科学
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催化化学
·
光催化
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Fangfang Li,Xiaofang Hou,Wei Fu,Jinjin Wang,Ying-Hua Zhou
The efficient transformation of CO 2 into high-value chemicals remains a significant challenge, particularly in the design of heterocatalysts capable of simultaneous multi-site activation towards the substrate. In this work, we develop the novel Zr-MOF catalysts incorporating both cobalt(II) meso-tetra(4-carboxyphenyl)porphine (CoTCPP) complex and the imidazolium bromide-based ionic liquid (IL) containing different alkyl chain (RImBr), where R = Et, Pr, Bu, and Pe), denoted as CoTCPP-UiO-66-IL(RImBr). The catalysts were synthesized through a solvothermal method followed by a post-synthetic modification. Among the prepared catalysts, CoTCPP-UiO-66-IL(BuImBr) demonstrated exceptional performance on the solventless and cocatalyst-free conversion of epichlorohydrin into chloropropene carbonate, achieving a remarkable 99% yield under mild conditions (90 °C and 1.0 bar CO 2 ). This outstanding catalytic efficiency was attributed to the synergistic effects of the dual Lewis-acid active sites offered by Zr-MOF node and the integrated CoTCPP complex, the strong nucleophilicity resulting from the incorporated imidazolium bromide-type IL, and the improved CO 2 adsorption capacity. Additionally, the CoTCPP-UiO-66-IL(BuImBr) catalyst exhibited excellent recyclability and broad substrate versatility in epoxide cycloaddition. These findings provide valuable insights into the development of multifunctional MOF-based heterogeneous catalysts with high activity and sustainability for CO 2 conversion applications.
研究领域:
材料科学
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催化化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Yongjian Wei,Ying Li,Yunfei Xu,Yuze Zu,Yinghui Sun,Tong Xu,Haiou Liang,Jie Bai
Exploring the impact of metal oxide crystal facets on the cycloaddition reaction of CO 2 with epoxides is meaningful because pure metal oxides exposing specific crystal facets show considerable promise as catalysts for industrial applications. In this study, we developed a simple strategy to prepare single-crystal ZnO nanosheet materials with controllable crystal facets through hydrothermal synthesis, followed by pyrolysis under different atmospheres. Studies revealed that the formation of ZnO single-crystal nanosheets involves the decomposition of the precursors and an ordered phase transition. Based on the quantitative correlation between oxygen vacancies, surface Zn, and the catalytic activity of ZnO (002) with varying numbers of oxygen vacancies, together with TPD, Py-IR, in-situ EPR, fluorescence spectroscopy characterizations, and DFT calculations, a synergistic mechanism between oxygen vacancies and surface Zn was proposed. Specifically, oxygen vacancies are the active sites for CO 2 , whereas saturated coordination surface Zn atoms activate epoxides. At 125 °C, 2 MPa, and 4 h, 93.3 % yield of the product was achieved using only 5 mg of the optimal ZnO catalyst. The excellent performance, stability, and applicability of single-crystal nanosheets make them ideal candidates for industrial applications. This study provides a new insight into the catalytic mechanisms of CO 2 cycloaddition over metal oxides.
研究领域:
材料科学
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催化化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2024
·
IF 4.1
Xiao-Shuang Cai,Hui-Xian Guo,Xiao-Juan Zhao,Jia-Ju Zhao,Hua-Min Liu,Sébastien Leveneur,Xue-De Wang
The cycloaddition of CO 2 to epoxidized molecules is an ecofriendly strategy for synthesizing aliphatic carbonates. In this study, heterogeneous catalytic synthesis of carbonated methyl oleate was performed. Influences of reaction parameters such as reaction temperature (403.15–443.15 K), pressure (1–3 MPa), concentration of functional groups (1.22–2.88 mol·L −1 ) and catalyst loading (0.025–0.042 g·mL −1 ) on the kinetics were evaluated. Gas-liquid mass transfer of CO 2 in the methylated oleic acid system was investigated, and a mathematical model was developed. The dissolution of CO 2 was found to be exothermic, and the dissolution capacity decreases with increasing temperature and decreasing pressure. The solubility of CO 2 follows an order of methylated form > epoxidized form > carbonated form. A high conversion rate (68.45 %) of epoxides was achieved in 6 h at 443.15 K and 3 MPa with a catalyst loading of 0.042 g·mL −1 . These results show a potential route for synthesizing aliphatic carbonates by combining methyl oleate with CO 2 .
研究领域:
化学工程
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of CO2 Utilization
·
2022
·
IF 8.321
Ye Qu,Yanglin Chen,Yifei Ye,Ping Xu,Jianmin Sun
Heterogenization of homogeneous catalysts without the loss of activity is still a huge challenge. Herein, homogeneous [HTMG][His][I] amino acid ionic liquid (IL), consisting of 1,1,3,3-tetramethylguanidine cation, histidine anion and iodine anion, were introduced into the pore channels of SBA-15 substrate with the assistance of supercritical CO 2 (scCO 2 ) media. Due to its low viscosity, high diffusivity and absence of surface tension, scCO 2 enabled [HTMG][His][I] to highly disperse in SBA-15 pore channels. Surprisingly, [HTMG][His][I]/SBA-15 heterogeneous catalyst displayed higher CO 2 cycloaddition activity (95% propylene carbonate yield) than equivalent molar pristine [HTMG][His][I] homogeneous catalyst (69% propylene carbonate yield) under the identical conditions. The significantly enhanced activity was resulted from the synergistic effect of [HTMG][His][I] and SBA-15 support. Moreover, [HTMG][His][I]/SBA-15 performed outstanding universality of various epoxides and reusability. This work developed a promising strategy to heterogenization of homogeneous IL catalyst assisted by scCO 2 as synthetic media and provided an efficient catalyst for CO 2 conversion.
研究领域:
化学工程
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催化材料
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绿色化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Yong Xu,Ping Wang,Xiaojun Zhan,Weili Dai,Qing Li,Jianping Zou,Xubiao Luo
Nowadays, it is becoming increasingly urgent to lower the escalating carbon dioxide (CO 2 ) to reduce greenhouse effect. Fortunately, it is an ideal strategy by using the inexhaustible solar energy as the driving force to manipulate the cycloaddition reaction, the atomic efficiency of which is 100 %. This work represents the first attempt on utilization of rare-earth metal Tb with atomic dispersion, and the structure of Tb coordinated with 4 N -atoms and 2B-atoms was constructed on interconnected carbon hollow spheres. The introduction of electron-deficient B reduces the electron density of Tb, thereby boosting Lewis acidity and promoting the occurrence of ring-opening reaction. The mechanism exploration enunciates that TbN 4 B 2 /C is a photothermal synergistic catalyst, the combined action of photogenerated electrons and strong Lewis acidic site of Tb reduces the free energy of the rate-determining step, and then improving the yield of cyclic carbonate up to 739 mmol g -1 h −1 .
研究领域:
环境科学
·
材料科学
·
化学工程
·
可再生能源
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of CO2 Utilization
·
2022
·
IF 8.321
Chengyuan Duan,Yuming Xie,Meili Ding,Yi Feng,Jianfeng Yao
Integrating dual Lewis acid and base as well as rational hierarchical pore structure in one catalyst is favorable to significantly boost the CO 2 cycloaddition reaction at mild conditions. In this regard, carbonized melamine sponge (CMS) featuring a highly porous network, rich nitrogen doping and excellent photothermal capability is employed as the ideal host for the construction of CMS@MOFs (namely, MIL-88-NH 2 and ZIF-8-NH 2 ) composites with diverse acid-base properties. Results show that all the obtained composites exhibited a satisfactory CO 2 adsorbing capacity (33–54 cm 3 /g) and delivered a remarkable yield of target cyclic carbonate at either mild thermal conditions (0.1 MPa CO 2 and 80 o C) or under light irradiation (light intensity: ~350 mW/cm 2 ) at room temperature. Even with diluted CO 2 (15 vol. % CO 2 ), high yields of 80–82 % are achievable. Moreover, the used catalysts can be easily recycled from reaction systems, leading to a good recyclability .
研究领域:
材料科学
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催化化学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Optical Materials
·
2025
·
IF 3.8
Yan Zhang,Junzhe Wang,Liang Li,Honggang Zhang,Bei Li,Xiangxiang Zhang,Zeyan Wang,Yuanyuan Liu,Peng Wang,Hefeng Cheng,Ying Dai,Baibiao Huang,Zhaoke Zheng
The design of organic–inorganic heterojunctions can facilitate the separation of photoinduced charge carriers by modulating the electronic structure at the surface and interface states, showing promising applications in the field of photocatalytic CO2 cycloaddition. However, the details of the surface/interface effects between these two components are still poorly understood. Herein, Cu2O@Cu3(HHTP)2 (HHTP = 2, 3, 6, 7, 10, 11-hexahydroxytriphenylene) heterojunctions were synthesized, where Cu2O nanoparticles (NPs) featuring distinct crystal facets were utilized as substrates for the in situ growth of the copper-based metal–organic framework (Cu3(HHTP)2). Among them, t-Cu2O@Cu3(HHTP)2, centered on t-Cu2O with {111} and {100} facets, exhibits superior performance toward photocatalytic CO2 cycloaddition to chlorinated propylene carbonate, with a conversion efficiency of 372 mmol g–1 h–1 under light. Notably, single-particle spectroscopy reveals a more efficient photogenerated carrier transfer between t-Cu2O and Cu3(HHTP)2. The results confirm that crystalline facet dependence is a key factor in semiconductor photocatalysis and an important strategy for optimizing the reactivity of photocatalysts, which provides a way to improve the photocatalytic CO2 cycloaddition performance by modulating the interfacial states of organic–inorganic heterojunction structures.
研究领域:
材料科学
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催化化学
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物理化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2022
·
IF 8.047
Yi Liu,Ying Chen,Yunli Liu,Zewen Chen,Huan Yang,Zhongxiao Yue,Qing Fang,Yunfei Zhi,Shaoyun Shan
Solar energy is considered as the cleanest, cheapest, and most sustainable energy source, and CO 2 cycloaddition that is drove by solar energy has unique advantages in the aspect of energy and environmental. Therefore, Zn and N co-doped porous carbon nanosheets (ZNCs), which were synthesized by a simple one-step pyrolysis method, as catalysts and photothermal material to photothermally drive cycloaddition of CO 2 . The prepared ZNCs show graphene-like layered structure, uniformly distributed Lewis acid (Zn atoms) sites and Lewis base (N atoms) sites, full spectrum absorption and high photothermal conversion efficiency. More importantly, ZNCs have a higher catalytic efficiency than traditional heating methods because it can be quickly in-situ heated by light, hence the yield of cyclic carbonate reached 91.1% (0.1 MPa CO 2 , 1000 mW·cm −2 full-spectrum irradiation, 12 h). ZNCs were recycled five times without significant reduction in catalytic efficiency, and have high activity to other series of epoxides. A possible CO 2 cycloaddition mechanism which is catalyzed by ZNCs is proposed, including the step of adsorption, ring opening, insertion and cyclic carbonates formation.
研究领域:
化学
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED ORGANOMETALLIC CHEMISTRY
·
2017
·Vol. 32
·期 2
·e4062
·
IF 2.319
Bibimaryam Mousavi,Somboon Chaemchuen,Chizoba I. Ezugwu,Ye Yuan,Francis Verpoort
We demonstrate the synthesis of isostructural zeolitic imidazole framework (ZIF-8) using four distinct synthetic methods. Subsequently, the variations in physicochemical properties were analyzed through the catalytic reaction of CO 2 cycloaddition of epoxide. It was thus demonstrated that simply by changing the type of synthetic method for the preparation of ZIF-8, the physicochemical properties were changed significantly which in turn influenced the catalytic activity of ZIF-8. It was found that the synthetic method affected the crystal growth and consequently influenced the physicochemical properties which are crucial aspects in metal–organic framework applications. There is an almost exponential relationship between the reactivity of various ZIF-8 samples in CO 2 cycloaddition of epoxide and the surface area, CO 2 adsorption and pore volume.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Fangfang Zhang,Yingxuan Wen,Falong Shan,Jingru Dou,Shougui Wang,Jipeng Dong,Guanghui Chen,Fei Gao
In this study, a sequence of pyridine-based hypercrosslinked ionic polymers (HIP-IBy, HIP-IByCA and HIP-IByBA) as heterogeneous catalysts were prepared using a two-step method for the CO 2 cycloaddition reaction. The synthesized pyridine-based HIPs exhibit rich and uniform mesoporous structures, and abundant nucleophilic halide ions and hydrogen bond donors are successfully integrated into the HIPs skeleton. The prepared catalysts show the superior CO 2 selective adsorption performance. In addition, the optimal catalyst HIP-IByBA(1:2) exhibits an excellent catalytic activity for the CO 2 cycloaddition without the metals, cocatalysts and solvents. Especially, under the mild condition (70 °C, 1.0 MPa), the catalyst HIP-IByBA(1:2) also maintains a satisfactory catalytic performance, effectively capturing dilute CO 2 (85 %N 2 /15 %CO 2 ) and converting it into cyclic carbonates. The excellent catalytic activity as well as good recyclability and substrate universality makes prepared pyridine-based HIPs promising heterogeneous catalysts for CO 2 cycloaddition reactions.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）