Facets-controllable synthesis of metal-organic frameworks via one supersaturation strategy to insight intrinsic facets effect

doi:10.1016/S1872-2067(25)64719-X

Abstract

Abstract:

The facets effect on the catalytic properties of inorganic compounds and metal-organic frameworks (MOFs) has been widely demonstrated, but the intrinsic facets effect free of interference of capping agents has not been discussed. Here we give a proof-of-concept illustration on the intrinsic facets effect by employing the popularly investigated NH₂-MIL-125(Ti) MOFs with {001}, {111} and {100} facets controllably exposed as model photocatalysts, which were synthesized via a simple supersaturation strategy free of any capping agents. Compared to conventional synthetic routes with capping agents employed, the NH₂-MIL-125(Ti) MOFs obtained in this work exhibit remarkably different physical and chemical properties such as surface wettability, charge separation as well as trend of facets effect on photocatalytic water splitting performance. The main reason has been unraveled to originate from unavoidable residue/influence of capping agents during the conventional facets-controlled synthetic routes leading to changed local surface structural environment as well as distinct charge separation property. Our results demonstrate the importance and feasibility of facets-controllable synthesis free of capping agents in getting insight into the intrinsic facets effect of MOFs-related materials.

Key words: Metal-organic framework, Facets-controllable synthesis, Supersaturation, Intrinsic facets effect, Photocatalyst

Lifang Liu, Yejun Xiao, Xiangyang Guo, Shengye Jin, Fuxiang Zhang. Facets-controllable synthesis of metal-organic frameworks via one supersaturation strategy to insight intrinsic facets effect[J]. Chinese Journal of Catalysis, 2025, 73: 153-158.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64719-X

https://www.cjcatal.com/EN/Y2025/V73/I6/153

Figures/Tables 5

Scheme 1. Schematic illustration for the synthesis NH2-MIL-125(Ti) of supersaturation-dependent facets evolution.

Fig. 1. SEM images of NH2-MIL-125(Ti) samples with different facets exposed under different preparative conditions. (a1)-(a4) Different volume ratios of DMF and MeOH are 9:1, 6:1, 4.5:1, and 1:1, respectively. Adding NaOH (aq, pH = 8): 1 μL (b1), 2 μL (b2), 4 μL (b3), and CH3COONa (4 mg) (b4). Changing the amount of Ti(C3H7O)4: 90 μL (c1), 100 μL (c2), 101 μL (c3), and 102 μL (c4).

Fig. 2. Comparison of the photocatalytic hydrogen evolution activity of the series samples prepared by different strategies: supersaturation strategy (a), capping agents (b,c), the photocatalytic reaction conditions of all the samples remain consistent.

Fig. 3. Comparison of structure properties of Ti111-OH, Ti111-OH-AA, and Ti111-OH-CTAB samples. (a) IR spectra; (b) Contact angle measurement; (c) X-ray photoelectron spectroscopy.

Fig. 4. UV-vis diffuse reflectance spectra (a), electrochemical impedance spectroscopy (b), and Comparison of normalized TA kinetics (c) of typical samples.

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