缺陷工程铟有机框架在温和条件下对二氧化碳与环氧化物的环化反应具有更高的吸附能力和更优异的催化性能。

IF 3.9 2区化学 Q2 CHEMISTRY, APPLIED

Molecular Diversity Pub Date : 2024-08-14 DOI:10.1007/s11030-024-10956-z

Meiyu Ren, Bo Zhao, Chong Li, Yang Fei, Xiaotong Wang, Liming Fan, Tuoping Hu, Xiutang Zhang

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引用次数: 0

摘要

为了实现对二氧化碳的高吸附和催化性能，直接自组装坚固的缺陷工程 MOFs 是一个鲜有报道且极具挑战性的命题。本文通过调节生长环境，生成了由链状[In(COO)2(H2O)]n和水状双核[In2(COO)4(H2O)8]两种无机单元组成的{[In2(CPPDA)(H2O)3](NO3)-2DMF-3H2O}n（NUC-107）高稳健纳米多孔铟（III）有机框架。值得一提的是，[In2(COO)4(H2O)8]的伴生水分子非常稀少，这意味着活化宿主框架中富含缺陷的金属离子可以充当强路易斯酸。与已报道的以[In4(μ3-OH)2(CPPDA)2(μ3-OH)2(DMF)(H2O)2]四核簇为节点的[In4(CPPDA)2(μ3-OH)2(COO)10(DMF)(H2O)2]n（NUC-66）骨架相比，NUC-107 的空隙体积（50.7%）略低于 NUC-66（52.8%）。然而，NUC-107 中每个 In3+ 离子平均有 1.5 个配位小分子（H2O），远远超过 NUC-66 中平均 0.75 个配位小分子（H2O 和 DMF）。热活化后，NUC-107a 具有不饱和 In3+ 位点、游离吡啶分子、无溶剂纳米通道（10.2 × 15.7 Å2）等优点。吸附测试证明，NUC-107a 的主框架比 NUC-66（273 K 时为 91.2 cm3/g，298 K 时为 53.0 cm3/g）具有更高的二氧化碳吸附能力（273 K 时为 113.2 cm3/g，298 K 时为 64.8 cm3/g）。催化实验证实，活化的 NUC-107a 在 n-Bu4NBr 的帮助下，能够在温和的条件下有效地催化 CO2 与环氧化物的环加成反应，生成相应的环碳酸盐。在 0.10 mol% MOFs、0.5 mol% n-Bu4NBr、0.5 MP CO2、60 °C 和 3 小时的类似条件下，与 NUC-66a 相比，NUC-107a 催化 SO 向 SC 的转化率提高了 21%。因此，这项工作提供了一个有价值的视角，即通过调节生长环境可以实现原位创建稳健的缺陷工程MOFs。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Defect-engineered indium-organic framework displays the higher CO2 adsorption and more excellent catalytic performance on the cycloaddition of CO2 with epoxides under mild conditions.

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Defect-engineered indium-organic framework displays the higher CO₂ adsorption and more excellent catalytic performance on the cycloaddition of CO₂ with epoxides under mild conditions.

In order to achieve the high adsorption and catalytic performance of CO₂, the direct self-assembly of robust defect-engineered MOFs is a scarcely reported and challenging proposition. Herein, a highly robust nanoporous indium(III)-organic framework of {[In₂(CPPDA)(H₂O)₃](NO₃)·2DMF·3H₂O}_n (NUC-107) consisting of two kinds of inorganic units of chain-shaped [In(COO)₂(H₂O)]_n and watery binuclear [In₂(COO)₄(H₂O)₈] was generated by regulating the growth environment. It is worth mentioning that [In₂(COO)₄(H₂O)₈] is very rare in terms of its richer associated water molecules, implying that defect-enriched metal ions in the activated host framework can serve as strong Lewis acid. Compared to reported skeleton of [In₄(CPPDA)₂(μ₃-OH)₂(DMF)(H₂O)₂]_n (NUC-66) with tetranuclear clusters of [In₄(μ₃-OH)₂(COO)₁₀(DMF)(H₂O)₂] as nodes, the void volume of NUC-107 (50.7%) is slightly lower than the one of NUC-66 (52.8%). However, each In³⁺ ion in NUC-107 has an average of 1.5 coordinated small molecules (H₂O), which far exceeds the average of 0.75 in NUC-66 (H₂O and DMF). After thermal activation, NUC-107a characterizes the merits of unsaturated In³⁺ sites, free pyridine moieties, solvent-free nanochannels (10.2 × 15.7 Å²). Adsorption tests prove that the host framework of NUC-107a has a higher CO₂ adsorption (113.2 cm³/g at 273 K and 64.8 cm³/g at 298 K) than NUC-66 (91.2 cm³/g at 273 K and 53.0 cm³/g at 298 K). Catalytic experiments confirmed that activated NUC-107a with the aid of n-Bu₄NBr was capable of efficiently catalyzing the cycloaddition of CO₂ with epoxides into corresponding cyclic carbonates under the mild conditions. Under the similar conditions of 0.10 mol% MOFs, 0.5 mol% n-Bu₄NBr, 0.5 MP CO₂, 60 °C and 3 h, compared with NUC-66a, the conversion of SO to SC catalyzed by NUC-107a increased by 21%. Hence, this work offers a valuable perspective that the in situ creation of robust defect-engineered MOFs can be realized by regulating the growth environment.

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来源期刊

Molecular Diversity 化学-化学综合

CiteScore

7.30

自引率

7.90%

发文量

219

审稿时长

2.7 months

期刊介绍： Molecular Diversity is a new publication forum for the rapid publication of refereed papers dedicated to describing the development, application and theory of molecular diversity and combinatorial chemistry in basic and applied research and drug discovery. The journal publishes both short and full papers, perspectives, news and reviews dealing with all aspects of the generation of molecular diversity, application of diversity for screening against alternative targets of all types (biological, biophysical, technological), analysis of results obtained and their application in various scientific disciplines/approaches including: combinatorial chemistry and parallel synthesis; small molecule libraries; microwave synthesis; flow synthesis; fluorous synthesis; diversity oriented synthesis (DOS); nanoreactors; click chemistry; multiplex technologies; fragment- and ligand-based design; structure/function/SAR; computational chemistry and molecular design; chemoinformatics; screening techniques and screening interfaces; analytical and purification methods; robotics, automation and miniaturization; targeted libraries; display libraries; peptides and peptoids; proteins; oligonucleotides; carbohydrates; natural diversity; new methods of library formulation and deconvolution; directed evolution, origin of life and recombination; search techniques, landscapes, random chemistry and more;