Synergy of single-atom iron and titanium-oxo cluster at oxygen vacancy in MIL-125-NH2 to achieve high-performance CO2-to-CH3OH photocatalysis

IF 13.3 1区工程技术 Q1 ENGINEERING, CHEMICAL

Chemical Engineering Journal Pub Date : 2025-04-18 DOI:10.1016/j.cej.2025.162811

Yan Che, Changyan Zhu, Xin Liu, Mengying Li, Xingbing Liu, Hongzhu Xing

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引用次数: 0

Abstract

Photocatalytic CO₂-to-CH₃OH is desirable to solve confronting issues of energy supply and carbon neutrality. However, the current CH₃OH production using photocatalyst needs promotion of reaction efficiency and product selectivity. We report herein the coupling of single-atom catalysis and oxygen vacancy-mediated photocatalysis in MIL-125-NH₂ to achieve high photocatalytic performance. We use the straightforward method of low-temperature thermolysis to control the OV content in the MOF, followed by post-synthetic ligation of Fe SAs under mild conditions to prepare a new photocatalyst of Fe@MIL-OV-300. It exhibits an excellent CH₃OH productivity of 3.96 mmol·g⁻¹·h⁻¹ that is among the topmost values reported so far. Mechanism studies by in-situ spectroscopy and theoretical calculation display the synergetic effect between Fe SA and Ti-oxo cluster at OV site to promote the highly efficient and selective CH₃OH generation. The study provides a new strategy to develop advanced photocatalyst with excellent performance for CO₂ reduction to value-added products.

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MIL-125-NH2中氧空位处单原子铁和钛氧团簇协同作用实现高性能CO2-to-CH3OH光催化

光催化CO2-to-CH3OH是解决能源供应和碳中和问题的理想选择。但目前光催化生产CH3OH还需要提高反应效率和产物选择性。本文报道了MIL-125-NH2中单原子催化和氧空位介导光催化的耦合，以获得高的光催化性能。我们采用直接的低温热裂解法来控制MOF中OV的含量，然后在温和的条件下将Fe - sa进行合成后的结扎，制备了新型的Fe@MIL-OV-300光催化剂。CH3OH产率为3.96 mmol·g−1·h−1，是目前报道的最高产率之一。原位光谱和理论计算的机理研究表明，OV位点的Fe SA和Ti-oxo簇之间存在协同作用，促进了CH3OH的高效选择性生成。该研究为开发具有优异性能的新型光催化剂制备高附加值产品提供了新的思路。

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来源期刊

Chemical Engineering Journal 工程技术-工程：化工

CiteScore

21.70

自引率

9.30%

发文量

6781

审稿时长

2.4 months

期刊介绍： The Chemical Engineering Journal is an international research journal that invites contributions of original and novel fundamental research. It aims to provide an international platform for presenting original fundamental research, interpretative reviews, and discussions on new developments in chemical engineering. The journal welcomes papers that describe novel theory and its practical application, as well as those that demonstrate the transfer of techniques from other disciplines. It also welcomes reports on carefully conducted experimental work that is soundly interpreted. The main focus of the journal is on original and rigorous research results that have broad significance. The Catalysis section within the Chemical Engineering Journal focuses specifically on Experimental and Theoretical studies in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. These studies have industrial impact on various sectors such as chemicals, energy, materials, foods, healthcare, and environmental protection.