Rapid and Green Mechanochemical Synthesis of UTSA-16(Zn) for High-Performance CO2 Capture★

doi:10.6023/A25120420

Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (5): 631-637.DOI: 10.6023/A25120420 Previous Articles Next Articles

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快速、绿色机械化学合成UTSA-16(Zn)用于高效碳捕获^★

王炙韬^a^,^†, 林雨珂^a^,^†, 万妍^a, 黄鑫伟^a, 李云斌^a, 吉定豪^b^,^*(), 项生昌^a^,^*(), 张章静^a^,^*()

^a 福建师范大学化学与材料学院福建省高分子材料重点实验室福州 350117
^b 中国航天员科研训练中心人因工程全国重点实验室北京 100094

投稿日期:2025-12-25 发布日期:2026-02-28
通讯作者: 吉定豪, 项生昌, 张章静
作者简介:
^† 共同第一作者
★“框架材料化学”专辑
基金资助:
国家杰出青年科学基金(22425102); 国家自然科学基金(22271046); 国家自然科学基金(22373015); 国家自然科学基金(22501044); 国家自然科学基金(W2431013); 人因工程全国重点实验室资金(HFNKL2023WW04)

Rapid and Green Mechanochemical Synthesis of UTSA-16(Zn) for High-Performance CO₂ Capture^★

Zhitao Wang^a, Yuke Lin^a, Yan Wan^a, Xinwei Huang^a, Yunbin Li^a, Dinghao Ji^b^,^*(), Shengchang Xiang^a^,^*(), Zhangjing Zhang^a^,^*()

^a Fujian Key Laboratory of Polymer Materials, College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350117, China
^b National Key Laboratory of Human Factors Engineering, China Astronaut Research and Training Center, Beijing 100094, China

Received:2025-12-25 Published:2026-02-28
Contact: Dinghao Ji, Shengchang Xiang, Zhangjing Zhang
About author:
^† These authors contributed equally to this work
★ For the VSI “Chemistry of Framework Materials”.
Supported by:
National Science Fund for Distinguished Young Scholars of China(22425102); National Natural Science Foundation of China(22271046); National Natural Science Foundation of China(22373015); National Natural Science Foundation of China(22501044); National Natural Science Foundation of China(W2431013); Foundation of National Key Laboratory of Human Factors Engineering(HFNKL2023WW04)

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Abstract

Addressing the pressing challenge of high energy consumption and solvent waste in the industrial-scale production of metal-organic frameworks (MOFs), we report a rapid, green, and scalable mechanochemical strategy for the mass preparation of the highly efficient CO₂ adsorbent, UTSA-16(Zn). Unlike conventional solvothermal methods, this protocol using zinc acetate and potassium citrate dramatically shortens the synthesis time from 48 h to just 6 h. This achieves a remarkable 48-fold enhancement in space-time yield while reducing solvent consumption by approximately 90%. Crucially, we identify that the in-situ accumulation of acidic byproducts during grinding inhibits framework assembly. Precise pH modulation using 0.2 equiv. of triethylamine (TEA) is essential to buffer the reaction environment, preventing defect formation and ensuring high product crystallinity. The resulting material is structurally isomorphous to its hydrothermally synthesized counterpart, possessing a consistent pore environment with a high BET surface area of 817 m²/g. In terms of performance, the mechanochemically derived UTSA-16(Zn) exhibits exceptional CO₂ uptake (3.68 mmol/g at 296 K and 0.1 MPa) and an ultra-high ideal adsorbed solution theory (IAST) selectivity of 388 for CO₂/N₂ mixtures, driven by a significant difference in isosteric heats of adsorption. Dynamic breakthrough experiments further validate a robust dynamic CO₂ capacity of 1.94 mmol/g and stable recyclability under simulated flue gas conditions. This work not only provides a practical manufacturing route for UTSA-16(Zn) but also underscores the pivotal role of pH regulation in the green synthesis of advanced porous materials.

Key words: UTSA-16, metal-organic frameworks (MOFs), separation, mechanochemical synthesis, carbon dioxide capture

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Zhitao Wang, Yuke Lin, Yan Wan, Xinwei Huang, Yunbin Li, Dinghao Ji, Shengchang Xiang, Zhangjing Zhang. Rapid and Green Mechanochemical Synthesis of UTSA-16(Zn) for High-Performance CO₂ Capture^★[J]. Acta Chimica Sinica, 2026, 84(5): 631-637.

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Fig. & Tab. 5

Figure 1. Schematic illustration of the mechanochemical synthesis for the mass preparation of UTSA-16(Zn)

Figure 2. Crystal structure of UTSA-16(Zn). (a) Coordination mode of the citrate ligand. Each ligand links a cubane-like (Zn(2)4O4) cluster, two tetrahedral Zn(1) units, and two K+ ions. Each K+ ion is coordinated by two water molecules (O(3W)). (b) The diamondoid cage features a pore window of 0.34 nm×0.58 nm. All metal ions are depicted as polyhedra with color coding consistent with (a). (c) Packing structure viewed along the b-axis. (d) GCMC simulations reveal two pairs of CO2 dimers trapped within the cage

Figure 3. (a) PXRD patterns of UTSA-16(Zn) synthesized with varying molar equivalents of triethylamine (relative to zinc acetate). (b) Product yield and FWHM of the peak at 2θ=7.48° as a function of triethylamine dosage. (c) PXRD patterns of samples prepared with different milling times. (d) Product yield and FWHM (2θ=7.48°) plotted versus milling time

Figure 4. Gas adsorption performance of mechanochemically synthesized UTSA-16(Zn). (a) N2 adsorption-desorption isotherms at 77 K (solid and open symbols represent adsorption and desorption, respectively). (b) Single-component CO2 and N2 adsorption isotherms at 273 K and 296 K. (c) IAST selectivity for a CO2/N2 (15∶85, V/V) mixture at 296 K. (d) Coverage-dependent adsorption enthalpy of CO2 and N2 calculated by the virial fitting method

Figure 5. Dynamic CO2/N2 separation performance and cycling stability of mechanochemically synthesized UTSA-16(Zn). Three consecutive breakthrough cycles for a CO2/N2 mixture (15∶85, V/V) at 296 K and 0.1 MPa with a total flow rate of 4 mL/min. Red and gold symbols represent CO2 and N2, respectively. C/C0 denotes the normalized effluent concentration

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快速、绿色机械化学合成UTSA-16(Zn)用于高效碳捕获^★

Rapid and Green Mechanochemical Synthesis of UTSA-16(Zn) for High-Performance CO₂ Capture^★

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快速、绿色机械化学合成UTSA-16(Zn)用于高效碳捕获★