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MIL-125@TiO2
JOURNAL OF ALLOYS AND COMPOUNDS · 2022 · IF 6.371

Constructing oxygen vacancies and linker defects in MIL-125 @TiO2 for efficient photocatalytic nitrogen fixation

Libo Wang,Shiyu Wang,Mohan Li,Xue Yang,Fengyan Li,Lin Xu,Yongcun Zou

With the emergence of issues such as global warming and glaciers melting, reducing carbon emissions cannot be ignored. Ammonia can participate in the N element cycle in nature and has a huge market demand. In modern industry, the preparation of ammonia mainly relies on the Haber-Bosch process with huge energy consumption. Using clean photocatalytic method to prepare ammonia can alleviate the above problems. Here, the core-shell structure of MIL-125 @TiO 2 was prepared by post solvothermal method for photocatalytic nitrogen fixation . Linker defects can appear as active sites in the residual MIL-125, which forms an obvious mesoporous structure that accelerates the exchange of electron/mass and promotes the activation of N 2 . The shell structure constructed by thin TiO 2 nanosheets possesses a large specific surface area . And the oxygen vacancies active sites could be highly exposed for nitrogen adsorption and activation, so as to promote the occurrence of the photocatalytic reaction. The O−Ti−N covalent bond is established between the titanium-oxygen clusters in the peripheral of TiO 2 and the linker in MIL-125, which improves the effective separation of electron-hole pairs. The ammonia formation rate of MIL-125 @TiO 2 -2 h is 102.7 µmol g −1 h −1 under simulated sunlight, which is 8 times higher than that of MIL-125. This work provides a novel idea for the preparation of photocatalytic nitrogen fixation materials with controllable structure and multiple active sites.

研究领域: 材料化学 · 光催化 · 纳米材料 · 环境科学 · 能源化学 · 多相催化
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Confinement of Cu2O by in-situ derived NH2-MIL-125@TiO2 for synergetic photothermal-driven hydrogen evolution from aqueous-phase methanol reforming

Baofang Zhang,Ziyu Zengcai,Wenting Lin,Meijin Zhang,Yunhong Pi,Tiejun Wang

Photothermal synergism can effectively activate methanol at low operating temperature and significantly reduce the activation energy of the reaction, achieving more efficiently H 2 release from methanol reforming. Here, a novel hierarchical heterojunction that integrating photo- and thermal-active Cu 2 O catalytic species with in-situ derived NH 2 -MIL-125@TiO 2 framework was specifically designed for photothermal-driven aqueous phase reforming of methanol into H 2 . The afforded Cu 2 O/NH 2 -MIL-125@TiO 2 realized an outstanding photothermal H 2 production activity (apparent quantum efficiency of 22.3 % at 365 nm), ca. 13-times higher than that of thermocatalytic condition. Interestingly, the photothermal effect did confer the Cu 2 O/NH 2 -MIL-125@TiO 2 with unexpected activity at low temperature subsided to 100 °C and accelerated the activation of MeOH/H 2 O with an obvious reduction of activation energy from 82.62 kJ·mol −1 to 52.40 kJ·mol −1 .   The improvement of catalyst stability and the promotion of charge separation also contributed to a long-term photothermal H 2 evolution activity with average rate of 1.49x10 6 μmolg Cu -1 h −1 and a total turnover number (TON) up to 5971 in 63 h, almost 125-fold promotion compared with Cu 2 O.

研究领域: 催化 · 材料科学 · 化学工程 · 可再生能源
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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2018 ·Vol. 29 ·期 14 ·12045-12054 · IF 2.324

CdSe QDs sensitized MIL-125/TiO2@SiO2 biogenic hierarchical composites with enhanced photocatalytic properties via two-level heterostructure

Huang Zhaohui,Chen Hui,Zhao Lei,He Xuan,Fang Wei,Du Yingying,Li Weixin,Wang Guanghui,Zhang Fuqing

With increasing concern about the problems of environmental pollution and energy, the visible light photocatalytic for dye degradation is receiving considerable attention. CdSe quantum dot (CdSe QDs) sensitized MIL-125/TiO 2 @SiO 2 biogenic hierarchical materials (CMTS) has been fabricated through dual modification of CdSe with TiO 2 and MIL-125, that is the metal–organic framework (MOF) with Ti ions as metal centers and terephthalic acid as the organic ligand. The hierarchical porous heterostructured MIL-125/TiO 2 @SiO 2 composites are firstly obtained by a biogenic-templated method using rice husk as biomorphic. CdSe QDs as sensitizer is further deposited on MIL-125/TiO 2 @SiO 2 via a dipping method. This strategy applies CdSe, MIL-125, and TiO 2 undergo a two-level heterostructure, setting a stage for efficient charge separation. In addition, CMTS possesses a hierarchical porous structure in scale from micrometer to nanometer with high BET surface area. As a result, the CMTS can efficiently adsorption target, improving light harvesting and promoting degradation of organic waste from water. Meanwhile, Rhodamine B aqueous solution can be degraded more than 98% by CMTS in 100 min under visible light irradiation.

研究领域: 材料科学 · 环境科学
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CHEMICAL ENGINEERING JOURNAL · 2020 · IF 10.652

In-situ implantation of plasmonic Ag into metal-organic frameworks for constructing efficient Ag/NH2-MIL-125/TiO2 photoanode

Weicheng Cui,Jianpeng Shang,Hongye Bai,Jian Hu,Dongbo Xu,Jinrui Ding,Weiqiang Fan,Weidong Shi

Realizing a highly efficient catalytic activity for photoelectrochemical (PEC) water splitting has been becoming a key challenge for fabricating TiO 2 photoanode, due to its weak light-response ability and poor electrical conductivity. For the first time, we prepared the TiO 2 nanorods decorated with NH 2 -MIL-125 film, and subsequently in-situ implanted Ag nanoparticles (Ag NPs) into NH 2 -MIL-125 film by mild reduction process with the help of amine group. The synergistic effect between NH 2 -MIL-125 and Ag NPs is aimed at efficiently improving light-response and the overall conductivity of photoanode. The PEC performance of as-prepared Ag/NH 2 -MIL-125/TiO 2 hybrid-photoanode has been systemically investigated. The photocurrent density of optimal Ag/NH 2 -MIL-125/TiO 2 has reached 1.06 mA/cm 2 at 1.23 V (vs. RHE) under illumination (100 mW/cm 2 ), which is almost 4.42 times higher than that of pristine TiO 2 . The incident photon-to-electron conversion efficiency (IPCE) value of Ag/NH 2 -MIL-125/TiO 2 has been increased to 51.0% at 390 nm. Furthermore, the desirable charge injection ( η i n j e c t i o n ) of 96.4% and charge separation ( η s e p a r a t i o n ) efficiency of 33.1% have been achieved. The in-situ introduction of Ag NPs into NH 2 -MIL-125/TiO 2 heterostructure provides a novel model for understanding the synergistic effect between metal and MOF over PEC water splitting.

CAS / MDL: 10312-55-7
研究领域: 材料科学 · 光化学 · 纳米技术 · 催化
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JOURNAL OF MATERIALS RESEARCH · 2025 · IF 2.9

In situ construction of S-type core–shell NH2-MIL-125/TiO2 heterojunctions and mechanism for visible photodynamic antibacterial systems

Yang Wen,Wang Yujia,Gao Na,Zhu Zhengfa,Chen Yuanyuan,Wang Hao,Tang Xiaoning

Designing efficient visible light-driven photocatalytic antimicrobial agents presents significant challenges. In this study, S-shaped core–shell NH 2 -MIL-125/TiO 2 (NT-x) heterojunctions were constructed by simple in situ solvothermal method, as photocatalytic antimicrobial agents for efficient bactericidal use under visible light. Notably, 99.99% inhibition was achieved for both Escherichia coli and Staphylococcus aureus at low concentrations (0.02 and 0.035 mg mL −1 , respectively) after exposure to simulated sunlight for 20 min. Reasonable energy band configuration and built-in electric field of this structure provided improved photogenerated carrier transfer paths as well as enhanced separation and transport efficiency. Moreover, the core–shell structure enhanced the interaction between NH 2 -MIL-125 and TiO 2 , increased the total number of reactive sites, and promoted the efficient generation of reactive oxygen species. Finally, possible mechanisms for the inactivation of bacteria were discussed. This research offers new perspectives for the advancement of advanced metal–organic framework-based photocatalysts with antibacterial activity under visible light. Graphical abstract

CAS / MDL: 64-17-5 67-56-1 68-12-2
研究领域: 材料科学 · 光催化 · 环境化学 · 纳米技术 · 抗菌材料
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