Ke Yude, Fan Zixuan, Mao Jingwen
Institute of Oceanic and Environmental Chemical Engineering, State Key Lab Breeding Base of Green Chemical Synthesis Technology, Zhejiang University of Technology Hangzhou 310014 China
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Sun Yat-Sen University Guangzhou 510000 P. R. China.
RSC Adv. 2024 Sep 18;14(40):29464-29471. doi: 10.1039/d4ra05273k. eCollection 2024 Sep 12.
Membranes with catalytic function can provide an effective approach for simultaneously transforming reactants to industrial chemicals and separation. However, rational design of stable and high-quality catalytic membranes with controlled structure remains a big challenge. We report a strategy for confined encapsulation of ultrafine FeO nanoclusters in nitrogen and sulfur co-doped graphene-based membranes for continuous chemical conversion. By manipulation of the active ferric catalytic center and surrounding coordination atoms in doped rGO nanosheets, multiple coordination structures were provided to achieve improved catalytic properties. Angstrom-level confined interlayer structure (∼8 Å) was constructed by external pressurization of Fe/NS-rGO nanosheets on membrane substrate, and the adsorption energy of 4-nitrophenol (4-NP) molecule between Fe/NS-rGO layers was much stronger than that in traditional nanometer-level confined space due to extra interactions, achieving the catalytic efficiency with a high Turnover Frequency (TOF) value (1596.0 h). The prepared ultrathin Fe/NS-rGO catalytic membrane also exhibited excellent water flux and rejection rate for small dye molecules, as well as long-term separation activity toward naphthol green B (NgB) for at least 130 h. The progress offers a viable route to the rational design of high-quality catalytic membranes with tailored structures and properties for wide applications.
具有催化功能的膜可为将反应物同时转化为工业化学品和进行分离提供一种有效方法。然而，合理设计具有可控结构的稳定且高质量的催化膜仍然是一项巨大挑战。我们报道了一种策略，即将超精细FeO纳米团簇限域封装在氮和硫共掺杂的石墨烯基膜中以实现连续化学转化。通过操控掺杂的还原氧化石墨烯（rGO）纳米片中的活性铁催化中心及周围的配位原子，提供了多种配位结构以实现催化性能的提升。通过对膜基底上的Fe/NS-rGO纳米片进行外部加压构建了埃级限域层间结构（约8 Å），由于额外的相互作用，4-硝基苯酚（4-NP）分子在Fe/NS-rGO层间的吸附能远强于传统纳米级限域空间中的吸附能，从而以高周转频率（TOF）值（1596.0 h⁻¹）实现了催化效率。所制备的超薄Fe/NS-rGO催化膜对小染料分子还表现出优异的水通量和截留率，以及对萘酚绿B（NgB）至少130小时的长期分离活性。这一进展为合理设计具有定制结构和性能以实现广泛应用的高质量催化膜提供了一条可行途径。
