配位组装构筑的磁性核壳复合材料促进CO2高值催化转化

doi:10.1016/S1872-2067(23)64400-6

催化学报 ›› 2023, Vol. 48: 258-266.DOI: 10.1016/S1872-2067(23)64400-6

配位组装构筑的磁性核壳复合材料促进CO₂高值催化转化

李金鹏^a, 陈洁^a, 郑庆舒^a, 屠波^a^,^*(), 涂涛^a^,^b^,^c^,^*()

^a复旦大学化学系, 上海市分子催化和功能材料重点实验室, 上海200438
^b中国科学院上海有机所, 有机金属化学国家重点实验室, 上海200032
^c郑州大学化学学院, 绿色催化中心, 河南郑州450001

收稿日期:2023-01-12 接受日期:2023-01-27 出版日期:2023-05-18 发布日期:2023-04-20
通讯作者: * 电子信箱: botu@fudan.edu.cn (屠波), taotu@fudan.edu.cn (涂涛).
基金资助:
国家自然科学基金(21871059);国家自然科学基金(21861132002)

Magnetic core-shell composites accessed by coordination assembly boost catalytic CO₂ valorization

Jinpeng Li^a, Jie Chen^a, Qingshu Zheng^a, Bo Tu^a^,^*(), Tao Tu^a^,^b^,^c^,^*()

^aShanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200438, China
^bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
^cGreen Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou 450001, Henan, China

Received:2023-01-12 Accepted:2023-01-27 Online:2023-05-18 Published:2023-04-20
Contact: * E-mail: botu@fudan.edu.cn (B. Tu),taotu@fudan.edu.cn (T. Tu)
Supported by:
National Natural Science Foundation of China(21871059);National Natural Science Foundation of China(21861132002)

摘要/Abstract

摘要：

自负载策略作为一种理想的分子催化剂负载方法引起了研究者的广泛关注. 该制备策略会得到无定型的块状固体催化材料, 导致大量活性催化中心被包埋在材料基体内部, 使得反应底物难以靠近催化中心, 从而降低了材料的催化效率. 形貌调控被认为是增强固体催化材料活性和相应功能的有效策略之一. 其中, 球状形貌的磁性四氧化三铁纳米颗粒(Fe₃O₄ NPs)因其比表面积较大、来源广泛和较好的磁响应性能而被广泛应用. 在已知文献中, 催化剂往往是通过后修饰策略进行负载的, 但由于负载位点随机、配位模式不明确以及金属易流失等原因, 相应负载催化材料的催化活性大大降低. 利用配位组装策略对磁性纳米颗粒进行包覆是当前制备球状核壳型自负载复合催化材料的可行方法之一. 考虑到三维材料具有多孔结构和更大的比表面积, 有利于气体吸附和传质传热, 因此可以作为磁性纳米颗粒理想的包覆材料.
本文利用四齿咪唑盐和金属(铱或钯)前体, 通过原位配位组装包覆策略对Fe₃O₄ NPs直接进行包覆, 制备了一系列磁性核壳结构复合型自负载固体分子催化材料. 扫描电子显微镜和透射电子显微镜结果表明, 此类复合材料呈现出明显的球状核壳结构, 其中氮杂环卡宾金属配位聚合物均匀地包覆在磁性Fe₃O₄ NPs表面. 能量色散X射线光谱和球差电镜结果表明, 金属均匀分散在整个复合材料基质中. X射线光电子能谱显示, 包覆后金属的配位环境与相应均相催化剂没有明显改变. N₂和CO₂吸附结果表明, 本文催化材料相比于相应的无定型自负载催化材料具有更大的比表面积和更高的CO₂吸附能力. 利用CO₂加氢和脱氢反应对复合材料的催化性能进行测试, 均显示出优于相应均相催化剂和自负载催化材料的催化活性. 其中, 在CO₂加氢制备甲酸的反应中, 得到较好的多相催化体系转化数(1.69 × 10⁶ TON). 此外, 在甲酸铵脱氢反应中, 催化材料可以通过磁性回收循环使用超过11次. 进一步对Fe₃O₄ NPs和无定型自负载催化材料的简单物理混合物进行了活性测试, 发现只能得到与无定型自负载催化材料类似的催化效果, 表明球状核壳结构对复合材料催化性能具有提升作用. 综上, 本文不仅通过包覆策略实现了催化材料的形貌调控, 而且提升了自负载固体分子催化材料的催化性能, 为CO₂高值化和氢气的存储和释放提供了可能.

关键词: CO₂高值化, 配位组装, 形貌调控, N-杂环卡宾化合物, 磁性催化材料

Abstract:

Magnetic core-shell composites are readily accessed by encapsulating Fe₃O₄ nanoparticles with NHC-M (M = Ir, Pd) coordination assemblies, which function as solid molecular catalysts and exhibit enhanced catalytic activity compared to the corresponding bis-NHC-Ir molecules in both hydrogenation and dehydrogenation reactions related to CO₂. A record turnover number (TON: 1.69 × 10⁶) was achieved in the hydrogenation of CO₂ to formic acid. In addition, robust solid catalysts can be magnetically recovered and reused for more than 11 runs without obvious loss in activity and selectivity for the dehydrogenation of ammonium formate, even at 10^-6 mmol level catalyst loadings.

Key words: CO₂ valorization, Coordination assembly, Morphology tuning, N-heterocyclic carbene complex, Magnetic composite

李金鹏, 陈洁, 郑庆舒, 屠波, 涂涛. 配位组装构筑的磁性核壳复合材料促进CO₂高值催化转化[J]. 催化学报, 2023, 48: 258-266.

Jinpeng Li, Jie Chen, Qingshu Zheng, Bo Tu, Tao Tu. Magnetic core-shell composites accessed by coordination assembly boost catalytic CO₂ valorization[J]. Chinese Journal of Catalysis, 2023, 48: 258-266.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64400-6

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图/表 4

Fig. 1. Fabrication of core-shell and irregular bulky NHC-M (M = Ir, Pd) coordination assemblies by encapsulating (a) and direct assembly (b) with and without Fe3O4 NPs. (Im = imidazolium ring, BenIm = benzimidazolium ring).

Fig. 2. SEM, TEM and EDX mapping images of Fe3O4@NHC-Ir 1a (a)-(g), Fe3O4@NHC-Ir 1b (h)-(n), and Fe3O4@NHC-Pd 2 (o)-(w).

Fig. 3. (a) XPS spectra of freshly prepared and recovered Fe3O4@NHC-Ir 1b, NHC-Ir 3b and bis-NHC-Ir complex 5b. (b) Magnified HAADF-TEM image of Fe3O4@NHC-Ir 1b, in which the well-dispersed white dots represented iridium single-atoms; Magnetic hysteresis loops (c) and PXRD patterns (d) of Fe3O4 NPs, Fe3O4@NHC-Ir 1a-b, and Fe3O4@NHC-Pd 2.

Fig. 4. TON for Hydrogenation of CO2 to formate (a) and N-formylation of dimethylamine salt to DMF (b) obtained by core-shell catalyst Fe3O4@NHC-Ir 1b, coordination assembly NHC-Ir 3b and bis-NHC-Ir complex 5b. (c) Reusability of Fe3O4@NHC-Ir 1b in the dehydrogenation of ammonium formate.

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配位组装构筑的磁性核壳复合材料促进CO₂高值催化转化

Magnetic core-shell composites accessed by coordination assembly boost catalytic CO₂ valorization

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