Keng Xuan,Yanfeng Pu,Feng Li,Jing Luo,Ning Zhao,Fukui Xiao
A series of metal-organic frameworks MOF-808-X (6-connected) were synthesized by regulating the ZrOCl 2 ·8H 2 O/1,3,5-benzenetricarboxylic acid (BTC) molar ratio (X) and tested for the direct synthesis of dimethyl carbonate (DMC) from CO 2 and CH 3 OH with 1,1,1-trimethoxymethane (TMM) as a dehydrating agent. The effect of the ZrOCl 2 ·8H 2 O/BTC molar ratio on the physicochemical properties and catalytic performance of MOF-808-X was investigated. Results showed that a proper ZrOCl 2 ·8H 2 O/BTC molar ratio during MOF-808-X synthesis was fairly important to reduce the redundant BTC or zirconium clusters trapped in the micropores of MOF-808-X. MOF-808-4, with almost no redundant BTC or zirconium clusters trapped in the micropores, exhibited the largest surface area, micropore size, and the number of acidic-basic sites, and consequently showed the best activity among all MOF-808-X, with the highest DMC yield of 21.5% under the optimal reaction conditions. Moreover, benefiting from the larger micropore size, MOF-808-4 outperformed our previously reported UiO-66-24 (12-connected), which had even more acidic-basic sites and larger surface area than MOF-808-4, mainly because the larger micropore size of MOF-808-4 provided higher accessibility for the reactant to the active sites located in the micropores. Furthermore, a possible reaction mechanism over MOF-808-4 was proposed based on the in situ FT-IR results. The effects of different reaction parameters on DMC formation and the reusability of MOF-808-X were also studied.
Yuzhi Li,Bingxin Lu,Jinyu Wang,Yufa Zhao,Kaibo Wang
The Zr-based metal–organic frameworks (Zr-MOFs) exhibit remarkable catalytic efficacy in the detoxification of nerve agents and their simulants. However, their practical military applications remain limited due to the poor processability inherent to their powder morphology. In this study, we fabricated a flexible hierarchical FeCoOx@PAN@MOF-808-IMDC composite fiber membrane with synergistic catalytic effects through a two-step fabrication strategy: (1) in situ growth of MOF-808 on electrospun FeCoOx@PAN fibers, followed by (2) postsynthetic modification with 4,5-imidazoledicarboxylic acid (IMDC) ligands. Density functional theory (DFT) calculations reveal that IMDC grafting reduces both the adsorption energy of DMNP on Zr clusters and the activation barrier for bond cleavage, leading to significantly accelerated reaction rates. Consequently, the optimized FeCoOx@PAN@MOF-808-IMDC exhibits exceptional DMNP hydrolysis performance, achieving complete conversion within 1 min and an ultrafast half-life of 6 s, along with high durability. This work effectively addresses the application limitations of powdered Zr-MOFs in protective systems and provides a viable pathway for integrating MOF materials into protective equipment for nerve agent detoxification.
危险品化学品经营许可证（带存储）