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Acetate Ions Facilitated Immobilization of Highly Dispersed Transition Metal Oxide Nanoclusters in Mesoporous Silica

Nan WangKey Laboratory of Advanced Molecular Engineering Materials, Engineering Research Center for Titanium Based Functional Materials and Devices in Universities of Shaanxi Province, College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721013, P. R. ChinaXueping LiKey Laboratory of Advanced Molecular Engineering Materials, Engineering Research Center for Titanium Based Functional Materials and Devices in Universities of Shaanxi Province, College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721013, P. R. ChinaXiaoyan LianKey Laboratory of Advanced Molecular Engineering Materials, Engineering Research Center for Titanium Based Functional Materials and Devices in Universities of Shaanxi Province, College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721013, P. R. ChinaQian ZhuangKey Laboratory of Advanced Molecular Engineering Materials, Engineering Research Center for Titanium Based Functional Materials and Devices in Universities of Shaanxi Province, College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721013, P. R. ChinaJialu WangKey Laboratory of Advanced Molecular Engineering Materials, Engineering Research Center for Titanium Based Functional Materials and Devices in Universities of Shaanxi Province, College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721013, P. R. ChinaJin LiKey Laboratory of Advanced Molecular Engineering Materials, Engineering Research Center for Titanium Based Functional Materials and Devices in Universities of Shaanxi Province, College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721013, P. R. ChinaHuaming QianKey Laboratory of Advanced Molecular Engineering Materials, Engineering Research Center for Titanium Based Functional Materials and Devices in Universities of Shaanxi Province, College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721013, P. R. ChinaKangkang MiaoKey Laboratory of Advanced Molecular Engineering Materials, Engineering Research Center for Titanium Based Functional Materials and Devices in Universities of Shaanxi Province, College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721013, P. R. ChinaYan WangKey Laboratory of Advanced Molecular Engineering Materials, Engineering Research Center for Titanium Based Functional Materials and Devices in Universities of Shaanxi Province, College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721013, P. R. ChinaXiaolin LuoKey Laboratory of Advanced Molecular Engineering Materials, Engineering Research Center for Titanium Based Functional Materials and Devices in Universities of Shaanxi Province, College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721013, P. R. ChinaGuodong FengXi’an Key Laboratory of Sustainable Energy Materials Chemistry, College of Chemistry, Xi’an Jiaotong University, Xi’an 710049, P. R. China

2024en

ABI

Annotatsiya

The immobilization of tiny active species within inert mesoporous silica imparts a range of functions, enhancing their applicability. A significant obstacle is the spontaneous migration and aggregation of these species within the mesopores, which threaten their uniform distribution. To address this, we propose a postmodification method that involves grafting transition metal oxide nanoclusters into silica mesopores via interfacial condensation, catalyzed by acetate ions. Specifically, CuO nanoclusters, in the form of oligomeric [O1–x–Cu2–(OH) 2x]n2+, have a strong interaction with the silica framework. This interaction inhibits their growth and prevents mesopore blockage. Theoretical calculation results reveal that the acetate ion promotes proton transfer among various hydroxy species, lowering the free energy and thereby facilitating the formation of Cu–O–Si bonds. This technique has also been successfully applied to the encapsulation of four other types of transition metal oxide nanoclusters. Our encapsulation strategy effectively addresses the challenge of dispersing transition metal oxides in mesoporous silica, offering a straightforward and widely applicable method for enhancing the functionality of mesoporous materials.

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DOI: 10.1021/acs.inorgchem.4c00024

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