蒸气相辅助法制备MOF基材料的研究进展

doi:10.11949/0438-1157.20241221

摘要/Abstract

摘要：

金属有机骨架（MOFs）材料因其具有高的比表面积和孔隙率、可调的孔径、丰富多样的结构等优势在气体吸附分离、催化、传感等领域展现出巨大的应用潜力。然而，传统MOF材料的合成以溶剂热法为主，不仅要消耗大量高值有机溶剂，且生产过程能耗高、产量低、废液难处理，不符合化工绿色发展的要求。蒸气相辅助合成法具有溶剂用量小、反应流程少、周期短等优势，近年来在MOF材料合成与改性方面受到广泛关注，有望为MOF材料的合成提供一条绿色高效的新途径。综述了蒸气相辅助法制备MOF基材料的研究进展，阐述了该方法在MOF材料合成及改性领域的研究进展，展望了该方法的发展前景。

关键词: 金属有机骨架材料, 蒸气辅助, 合成, 经济, 改性, 绿色

Abstract:

Metal-organic framework materials (MOFs) have shown great potential in various applications, including gas adsorption and separation, catalysis, and sensing due to their high specific surface area and porosity, adjustable pore sizes, and diverse structures. However, the synthesis of traditional MOF materials is mainly based on solvothermal method, which not only consumes a large amount of high-value organic solvents, but also has high energy consumption, low yield, and difficult waste liquid treatment in the production process, which does not meet the requirements of green development of chemical industry. The steam-assisted synthesis, which has the advantages of small solvent dosage, fewer reaction processes and shorter cycle time, has received extensive attention in the synthesis and modification of MOF materials in recent years, and it is expected to provide a new green and efficient pathway for the synthesis of MOF materials. This paper reviews the research advancements of MOF prepared by steam-assisted method, overviews the research progress of this method in the synthesis and modification of MOF materials. Additionally, the prospective developments of this synthesis method are discussed.

Key words: metal-organic framework materials, steam-assisted, synthesis, economic, modification, green

中图分类号:

TQ 021.4

张冰, 李建惠, 马欣蓉, 陈杨, 李晋平, 李立博. 蒸气相辅助法制备MOF基材料的研究进展[J]. 化工学报, 2025, 76(5): 2026-2041.

Bing ZHANG, Jianhui LI, Xinrong MA, Yang CHEN, Jinping LI, Libo LI. Research progress of MOF preparation by steam-assisted method[J]. CIESC Journal, 2025, 76(5): 2026-2041.

图/表 16

图1 MOF材料的合成方法发展时间轴

Fig.1 Timeline of the development of synthesis methods for MOF materials

表1 MOF不同合成方法的总结

Table 1 Summary of different synthesis methods of MOF

合成方法	优点	缺点	MOF	比表面积/ (m²/g)	时空产率/ (kg/(m³·d))	文献
溶剂热合成法	适用范围广	高温高压、废液难以处理	MOF-5	2900	—	[18]
电化学合成法	合成效率高	能耗高、普适性差	Cu-MOF	1820	—	[23]
微波加热法	效率高，反应时间短	微波设备成本高	Ni-MOF-74	1252	—	[24]
			Mg-MOF-74	1416	—	[24]
			UiO-66	1052	7163	[30]
超声波化学法	快速结晶	产品质量低	MOF-1	—	—	[26]
微通道合成技术法	反应速率快	设备加工成本高、狭窄的通道易堵塞	MOF-808	1600	95000	[27]
室温溶液合成法	简单、廉价、绿色	单体溶解度差、普适性差	UiO-66-(COOH)₂	890	—	[22]
室温溶液合成法	简单、廉价、绿色	单体溶解度差、普适性差	HKUST-1	1749	1842	[31]
机械研磨法	环境友好、经济高效	产品质量低、稳定性差	ZIF-8	37	—	[28]

图2 蒸气相辅助法制备MOF的优势

Fig.2 Advantages of MOF preparation by steam-assisted method

图3 合成ZIF的反应容器示意图[33]

Fig.3 Diagram of reaction vessel for synthesis of ZIF[33]

图4 (a)蒸气相辅助法合成MIL-100(Fe)的装置示意图；(b)蒸气相辅助法与电合成的MIL-100(Fe)相对结晶度曲线对比[36]；(c)蒸气相辅助法合成UiO型MOF的装置示意图[37]；(d)蒸气相辅助法合成MIL-101的反应器图（左）和孔洞聚四氟乙烯板（左下），水的P-V相图（右）[40]

Fig.4 (a) Schematic diagram of the steam-assisted synthesis of MIL-100(Fe); (b) Relative crystallinity curves of MIL-100(Fe) by steam-assisted method and electrosynthesis[36]; (c) Schematic diagram of the device for the synthesis of UiO-type MOF by steam-assisted method[37]; (d) Reactor diagram of steam-assisted synthesis of MIL-101 (left) and holed-Teflon plate (left-bottom), P-V phase diagram of water (right)[40]

图5 (a)蒸气相辅助法合成MOF-74装置的内部结构[38]；(b)蒸气相辅助合成MOF-74的装置：金属氧化物（MO）和H4dobdc配体以2∶1的比例混合[39]；(c)ZnO与H4dobdc在不同蒸气条件下反应得到的产物[39]；(d)采用溶剂热合成法合成MIL-101的SEM图；(e)图(d)的局部放大；蒸气相辅助法合成MIL-101的SEM图：(f) Cr/H2BDC=1/1，(g) Cr/H2BDC=1/1.2[40]

Fig.5 (a) Diagram of the internal installation of the steam-assisted synthesis MOF-74[38]； (b) Steam-assisted synthesis of MOF-74∶metal oxide (MO) and H4dobdc ligand are mixed in a ratio of 2∶1[39]; (c) Products obtained by the reaction ZnO with H4 dobdc under different steam conditions[39]; (d) SEM image of MIL-101 synthesized by solvent-thermal synthesis method; (e) The expanded images of figure (d); SEM diagram of steam-assisted synthesis MIL-101： (f) Cr/H2BDC=1/1， (g) Cr/H2BDC=1/1.2[40]

图6 SEC和SAC合成中的溶剂循环过程示意图[45]

Fig.6 Schematic diagram of solvent cycle in SEC and SAC synthesis[45]

图7 ZIF-8薄膜的化学气相沉积流程图[54]

Fig.7 Flow diagram of chemical vapor deposition of ZIF-8 thin film[54]

图8 (a)化学气相沉积Cu基MOF薄膜流程示意图[55]；(b)气相辅助合成HKUST-1粉末（左）和HKUST-1膜的示意图（右）[56]；(c)蒸气相辅助反应制备大孔MAF-6粉末（上）和薄膜的合成示意图（下）[57]；(d)化学气相沉积法制备CAT-1膜装置流程图[58]

Fig.8 (a) Chemical vapor deposition Cu-based MOF film flow diagram[55]; (b) Steam-assisted synthesis of HKUST-1 powder (left) and HKUST-1 film (right)[56]; (c) Schematic diagram of preparation of large-pore MAF-6 powder (top) and thin film by steam-assisted method (bottom)[57]; (d) Flow chart of CAT-1 film device prepared by chemical vapor deposition[58]

图9 ZnO薄膜的制备并将其转化为MOF薄膜的示意图［SEM显微图像展示了Si（100）衬底上MOF形成的各个阶段］[59]

Fig.9 Schematic diagram of the preparation of ZnO thin film and conversion into MOF thin film［SEM microscopic images show the various stages of MOF formation on Si (100) substrate］[59]

图10 (a)CVD炉中Co(acac)2和2-MIM的蒸气流辅助反应在基质上生长ZIF-67的示意图；(b)ZIF-67化学电阻器的制备示意图；(c)ZIF-67沉积前和沉积后的电极光学图像；(d)CVD ZIF-67化学电阻器在不同环境条件下的气敏性；(e)CVD ZIF-67化学电阻器在不同湿度条件下的输出特性[60]

Fig.10 (a) Schematic diagram of the growth of ZIF-67 on substrate by the steam-flow assisted reaction of Co(acac)2 and 2-MIM in a CVD furnace; (b) Schematic diagram of preparation of ZIF-67 chemical resistor; (c) Optical images of ZIF-67 electrodes before and after deposition; (d) Gas sensitivity of CVD ZIF-67 chemical resistors under different environmental conditions; (e) Output characteristics of CVD ZIF-67 chemical resistor under different humidity conditions[60]

图11 (a)合成高质量Mg-MOF-74薄膜的CVD工艺示意图[62]；(b)真空反应装置中平衡过程[63]

Fig.11 (a) CVD process diagram for synthesizing high quality Mg-MOF-74 film[62]; (b) Overview of equilibrium processes in vacuum reaction units[63]

图12 (a)H-ZIF-8中产生分级多孔结构的空气-蒸气刻蚀工艺基本原理示意图；(b)ZIF-8和H-ZIF-8样品在环氧氯丙烷催化CO2环加成中的催化性能[69]；(c)蒸气刻蚀、溶液刻蚀制备HP-Cu-BTC的方法示意图及气体分离性能[70]

Fig.12 (a) Schematic diagram of the basic principle of the air-steam etching process for producing layered porous structures in H-ZIF-8; (b) Catalytic performance of ZIF-8 and H-ZIF-8 samples in the cycloaddition of CO2 catalyzed by epichlorohydrin[69]; (c) Method diagram of preparation of HP-Cu-BTC by steam etching and solution etching and gas separation performance diagram[70]

图13 (a)蒸气相辅助法合成HKUST-1的原理图；(b)、(c)分别为蒸气相辅助法和溶剂热法合成HKUST-1/Fe3O4复合材料的合成原理图；(d)HKUST-1/Fe3O4复合材料对噻吩和苯并噻吩（上）、吲哚和喹啉（下）的吸附性能[44]

Fig.13 (a) Schematic diagram of synthesis of HKUST-1 by steam-assisted method; (b),(c) Schematic diagram of synthesis of HKUST-1/Fe3O4 composites by steam-assisted and solvothermal methods; (d) Adsorption properties of HKUST-1/Fe3O4 composites for thiophene and benzothiophene (top), indole and quinoline (bottom)[44]

图14 蒸气相辅助合成后功能化（PSF）流程示意图[74]

Fig.14 Schematic diagram of the steam-assisted postsynthetic functionalization (PSF) process[74]

图15 (a)VPLE过程的示意图[76]；(b)多连接体VPLE策略示意图；(c) ZIF-8对CO2、CH4和N2的吸附等温线；(d) ZIF-8/I的气体吸附等温线；(e) ZIF-8/Cl的气体吸附等温线；(f) ZIF-8/Br的气体吸附等温线；(g) ZIF-8/I/Cl的气体吸附等温线；(h) ZIF-8和连接体交换的ZIF的CO2/N2和CH4/N2选择性[77]

Fig.15 (a) Schematic diagram of the VPLE process[76]; (b) Schematic diagram of multi-connector VPLE strategy; (c) The adsorption isotherm of CO2, CH4 and N2 by ZIF-8; (d) Gas adsorption isotherm of ZIF-8/I; (e) Gas adsorption isotherm of ZIF-8/Cl; (f) Gas adsorption isotherm of ZIF-8/Br; (g) Gas adsorption isotherm of ZIF-8/I/Cl; (h) CO2/N2 and CH4/N2 selectivity of ZIF exchanged between ZIF-8 and the linker[77]

参考文献 79

1	Yaghi O M, Li G M, Li H L. Selective binding and removal of guests in a microporous metal-organic framework[J]. Nature, 1995, 378: 703-706.
2	Yaghi O M, O'Keeffe M, Ockwig N W, et al. Reticular synthesis and the design of new materials[J]. Nature, 2003, 423(6941): 705-714.
3	Férey G. Hybrid porous solids: past, present, future[J]. Chemical Society Reviews, 2008, 37(1): 191-214.
4	Dutta S, Walden M, Sinelshchikova A, et al. Cradle-to-gate environmental impact assessment of commercially available metal-organic frameworks manufacturing[J]. Advanced Functional Materials, 2024, 34(52): 2410751.
5	崔希利, 邢华斌. 金属有机框架材料分离低碳烃的研究进展[J]. 化工学报, 2018, 69(6): 2339-2352.
	Cui X L, Xing H B. Separation of light hydrocarbons with metal-organic frameworks[J]. CIESC Journal, 2018, 69(6): 2339-2352.
6	李建惠, 兰天昊, 陈杨, 等. MOF复合材料在气体吸附分离中的研究进展[J]. 化工学报, 2021, 72(1): 167-179.
	Li J H, Lan T H, Chen Y, et al. Research progress of MOF-based composites for gas adsorption and separation[J]. CIESC Journal, 2021, 72(1): 167-179.
7	Zhang L, Yu B, Wang M, et al. Ethane triggered gate-opening in a flexible-robust metal-organic framework for ultra-high purity ethylene purification[J]. Angewandte Chemie International Edition, 2025, 64(7): e202418853.
8	Feng Y, Yan W, Kang Z X, et al. Thermal treatment optimization of porous MOF glass and polymer for improving gas permeability and selectivity of mixed matrix membranes[J]. Chemical Engineering Journal, 2023, 465: 142873.
9	Gao Z Z, Li B J, Li Z, et al. Free-standing metal-organic framework membranes made by solvent-free space-confined conversion for efficient H₂/CO₂ separation[J]. ACS Applied Materials & Interfaces, 2023, 15(15): 19241-19249.
10	Vikal A, Maurya R, Patel P, et al. Exploring metal-organic frameworks (MOFs) in drug delivery: a concise overview of synthesis approaches, versatile applications, and current challenges[J]. Applied Materials Today, 2024, 41: 102443.
11	Hou Q Q, Zhou S, Wei Y Y, et al. Balancing the grain boundary structure and the framework flexibility through bimetallic metal-organic framework (MOF) membranes for gas separation[J]. Journal of the American Chemical Society, 2020, 142(21): 9582-9586.
12	Lan T H, Li L B, Chen Y, et al. Opportunities and critical factors of porous metal-organic frameworks for industrial light olefins separation[J]. Materials Chemistry Frontiers, 2020, 4(7): 1954-1984.
13	Yang M X, Xiao L F, Chen W T, et al. Recent advances on metal-organic framework-based electrochemical sensors for determination of organic small molecules[J]. Talanta, 2024, 280: 126744.
14	Zhang Y, Yu X H, Hou Y W, et al. Current research status of MOF materials for catalysis applications[J]. Molecular Catalysis, 2024, 555: 113851.
15	Li H, Li L B, Lin R B, et al. Porous metal-organic frameworks for gas storage and separation: status and challenges[J]. EnergyChem, 2019, 1(1): 100006.
16	Felix Sahayaraj A, Joy Prabu H, Maniraj J, et al. Metal-organic frameworks (MOFs): the next generation of materials for catalysis, gas storage, and separation[J]. Journal of Inorganic and Organometallic Polymers and Materials, 2023, 33(7): 1757-1781.
17	Shi L, Zhong Y L, Cao H H, et al. A hetero-supermolecular-building-block strategy for the assembly of porous (3,12,24)-connected uru metal-organic frameworks[J]. Nature Synthesis, 2024, 3(12): 1560-1566.
18	Li H L, Eddaoudi M, O’Keeffe M, et al. Design and synthesis of an exceptionally stable and highly porous metal-organic framework[J]. Nature, 1999, 402: 276-279.
19	Han J L, He X D, Liu J, et al. Determining factors in the growth of MOF single crystals unveiled by in situ interface imaging[J]. Chem, 2022, 8(6): 1637-1657.
20	Li H, Qin Z, Yang X F, et al. Growth pattern control and nanoarchitecture engineering of metal-organic framework single crystals by confined space synthesis[J]. ACS Central Science, 2022, 8(6): 718-728.
21	Zhang P, Kang X C, Tao L M, et al. A new route for the rapid synthesis of metal-organic frameworks at room temperature[J]. CCS Chemistry, 2023, 5(6): 1462-1469.
22	Chen Z J, Wang X J, Noh H, et al. Scalable, room temperature, and water-based synthesis of functionalized zirconium-based metal-organic frameworks for toxic chemical removal[J]. CrystEngComm, 2019, 21(14): 2409-2415.
23	Mueller U, Schubert M, Teich F, et al. Metal-organic frameworks—prospective industrial applications[J]. Journal of Materials Chemistry, 2006, 16(7): 626-636.
24	Wu X F, Bao Z B, Yuan B, et al. Microwave synthesis and characterization of MOF-74 (M=Ni, Mg) for gas separation[J]. Microporous and Mesoporous Materials, 2013, 180: 114-122.
25	Ogura Y, Taniya K, Horie T, et al. Process intensification of synthesis of metal organic framework particles assisted by ultrasound irradiation[J]. Ultrasonics Sonochemistry, 2023, 96: 106443.
26	Qiu L G, Li Z Q, Wu Y, et al. Facile synthesis of nanocrystals of a microporous metal-organic framework by an ultrasonic method and selective sensing of organoamines[J]. Chemical Communications, 2008(31): 3642-3644.
27	Bagi S, Yuan S, Rojas-Buzo S, et al. A continuous flow chemistry approach for the ultrafast and low-cost synthesis of MOF-808[J]. Green Chemistry, 2021, 23(24): 9982-9991.
28	Katsenis A D, Puškarić A, Štrukil V, et al. In situ X-ray diffraction monitoring of a mechanochemical reaction reveals a unique topology metal-organic framework[J]. Nature Communications, 2015, 6: 6662.
29	Wang C, Zhang F F, Yang J F, et al. Rapid and HF-free synthesis of MIL-100(Cr) via steam-assisted method[J]. Materials Letters, 2019, 252: 286-288.
30	Taddei M, Casati N, Steitz D A, et al. In situ high-resolution powder X-ray diffraction study of UiO-66 under synthesis conditions in a continuous-flow microwave reactor[J]. CrystEngComm, 2017, 19(23): 3206-3214.
31	Majano G, Pérez-Ramírez J. Scalable room-temperature conversion of copper(Ⅱ) hydroxide into HKUST-1 (Cu₃(btc)₂)[J]. Advanced Materials, 2013, 25(7): 1052-1057.
32	Xu W Y, Dong J X, Li J P, et al. A novel method for the preparation of zeolite ZSM-5[J]. Journal of the Chemical Society, Chemical Communications, 1990(10): 755-756.
33	Shi Q, Chen Z F, Song Z W, et al. Synthesis of ZIF-8 and ZIF-67 by steam-assisted conversion and an investigation of their tribological behaviors[J]. Angewandte Chemie International Edition, 2011, 50(3): 672-675.
34	Horcajada P, Surblé S, Serre C, et al. Synthesis and catalytic properties of MIL-100(Fe), an iron(Ⅲ) carboxylate with large pores[J]. Chemical Communications, 2007(27): 2820-2822.
35	Seo Y K, Yoon J W, Lee J S, et al. Large scale fluorine-free synthesis of hierarchically porous iron(Ⅲ) trimesate MIL-100(Fe) with a zeolite MTN topology[J]. Microporous and Mesoporous Materials, 2012, 157: 137-145.
36	Ahmed I, Jeon J, Khan N A, et al. Synthesis of a metal-organic framework, iron-benezenetricarboxylate, from dry gels in the absence of acid and salt[J]. Crystal Growth & Design, 2012, 12(12): 5878-5881.
37	Gökpinar S, Diment T, Janiak C. Environmentally benign dry-gel conversions of Zr-based UiO metal-organic frameworks with high yield and the possibility of solvent re-use[J]. Dalton Transactions, 2017, 46(30): 9895-9900.
38	Das A K, Vemuri R S, Kutnyakov I, et al. An efficient synthesis strategy for metal-organic frameworks: dry-gel synthesis of MOF-74 framework with high yield and improved performance[J]. Scientific Reports, 2016, 6: 28050.
39	Wauteraerts N, Tu M, Chanut N, et al. Vapor-assisted synthesis of the MOF-74 metal-organic framework family from zinc, cobalt, and magnesium oxides[J]. Dalton Transactions, 2023, 52(47): 17873-17880.
40	Kim J, Lee Y R, Ahn W S. Dry-gel conversion synthesis of Cr-MIL-101 aided by grinding: high surface area and high yield synthesis with minimum purification[J]. Chemical Communications, 2013, 49(69): 7647-7649.
41	Férey G, Mellot-Draznieks C, Serre C, et al. A chromium terephthalate-based solid with unusually large pore volumes and surface area[J]. Science, 2005, 309(5743): 2040-2042.
42	Latroche M, Surblé S, Serre C, et al. Hydrogen storage in the giant-pore metal-organic frameworks MIL-100 and MIL-101[J]. Angewandte Chemie International Edition, 2006, 45(48): 8227-8231.
43	Horcajada P, Serre C, Vallet-Regí M, et al. Metal-organic frameworks as efficient materials for drug delivery[J]. Angewandte Chemie International Edition, 2006, 45(36): 5974-5978.
44	Tan P, Xie X Y, Liu X Q, et al. Fabrication of magnetically responsive HKUST-1/Fe₃O₄ composites by dry gel conversion for deep desulfurization and denitrogenation[J]. Journal of Hazardous Materials, 2017, 321: 344-352.
45	Chen Y, Yang C Y, Wang X Q, et al. Vapor phase solvents loaded in zeolite as the sustainable medium for the preparation of Cu-BTC and ZIF-8[J]. Chemical Engineering Journal, 2017, 313: 179-186.
46	Liu Y T, Chen H, Li T, et al. Balancing the crystallinity and film formation of metal-organic framework membranes through in situ modulation for efficient gas separation[J]. Angewandte Chemie International Edition, 2023, 62(37): e202309095.
47	Wu M M, Sun Y W, Ji T T, et al. Fabrication of water-stable MOF-808 membrane for efficient salt/dye separation[J]. Journal of Membrane Science, 2023, 686: 122023.
48	Shah M, McCarthy M C, Sachdeva S, et al. Current status of metal-organic framework membranes for gas separations: promises and challenges[J]. Industrial & Engineering Chemistry Research, 2012, 51(5): 2179-2199.
49	Luo L X, Hou L X, Cui X P, et al. Self-condensation-assisted chemical vapour deposition growth of atomically two-dimensional MOF single-crystals[J]. Nature Communications, 2024, 15(1): 3618.
50	Fu M, Liu Y L, Lyu Q, et al. Sustainable vapor-phase deposition and applications of MOF films and membranes: a critical review[J]. Separation and Purification Technology, 2025, 356: 129883.
51	Choe M, Koo J Y, Park I, et al. Chemical vapor deposition of edge-on oriented 2D conductive metal-organic framework thin films[J]. Journal of the American Chemical Society, 2022, 144(37): 16726-16731.
52	Hachem K, Ansari M J, Saleh R O, et al. Methods of chemical synthesis in the synthesis of nanomaterial and nanoparticles by the chemical deposition method: a review[J]. BioNanoScience, 2022, 12(3): 1032-1057.
53	Salmi L D, Heikkilä M J, Puukilainen E, et al. Studies on atomic layer deposition of MOF-5 thin films[J]. Microporous and Mesoporous Materials, 2013, 182: 147-154.
54	Stassen I, Styles M, Grenci G, et al. Chemical vapour deposition of zeolitic imidazolate framework thin films[J]. Nature Materials, 2016, 15(3): 304-310.
55	Stassin T, Rodríguez-Hermida S, Schrode B, et al. Vapour-phase deposition of oriented copper dicarboxylate metal-organic framework thin films[J]. Chemical Communications, 2019, 55(68): 10056-10059.
56	Rodríguez-Hermida S, Kravchenko D E, Wauteraerts N, et al. Vapor-assisted powder synthesis and oriented MOF-CVD thin films of the metal-organic framework HKUST-1[J]. Inorganic Chemistry, 2022, 61(45): 17927-17931.
57	Stassin T, Stassen I, Marreiros J, et al. Solvent-free powder synthesis and MOF-CVD thin films of the large-pore metal-organic framework MAF-6[J]. Chemistry of Materials, 2020, 32(5): 1784-1793.
58	Mähringer A, Jakowetz A C, Rotter J M, et al. Oriented thin films of electroactive triphenylene catecholate-based two-dimensional metal-organic frameworks[J]. ACS Nano, 2019, 13(6): 6711-6719.
59	Medishetty R, Zhang Z J, Sadlo A, et al. Fabrication of zinc-dicarboxylate- and zinc-pyrazolate-carboxylate-framework thin films through vapour-solid deposition[J]. Dalton Transactions, 2018, 47(40): 14179-14183.
60	Huang J K, Saito N, Cai Y C, et al. Steam-assisted chemical vapor deposition of zeolitic imidazolate framework[J]. ACS Materials Letters, 2020, 2(5): 485-491.
61	Tu M, Kravchenko D E, Xia B Z, et al. Template-mediated control over polymorphism in the vapor-assisted formation of zeolitic imidazolate framework powders and films[J]. Angewandte Chemie International Edition, 2021, 60(14): 7553-7558.
62	Kim K J, Culp J T, Ohodnicki P R, et al. Synthesis of high-quality Mg-MOF-74 thin films via vapor-assisted crystallization[J]. ACS Applied Materials & Interfaces, 2021, 13(29): 35223-35231.
63	Gschwind W, McCarthy B D, Suremann N F, et al. The influence of water in the vapor-assisted conversion synthesis of UiO-67 MOF thin films[J]. European Journal of Inorganic Chemistry, 2023, 26(27): e202300216.
64	杨东晓, 熊启钊, 王毅, 等. 多级孔MOF的制备及其吸附分离应用研究进展[J]. 化工进展, 2024, 43(4): 1882-1896.
	Yang D X, Xiong Q Z, Wang Y, et al. Progress in the preparation of hierarchically porous MOF and applications in adsorption and separation[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 1882-1896.
65	Koo J, Hwang I C, Yu X J, et al. Hollowing out MOFs: hierarchical micro-and mesoporous MOFs with tailorable porosity via selective acid etching[J]. Chemical Science, 2017, 8(10): 6799-6803.
66	Xi D Y, Sun Q M, Xu J, et al. In situ growth-etching approach to the preparation of hierarchically macroporous zeolites with high MTO catalytic activity and selectivity[J]. Journal of Materials Chemistry A, 2014, 2(42): 17994-18004.
67	McNamara N D, Hicks J C. Chelating agent-free, vapor-assisted crystallization method to synthesize hierarchical microporous/mesoporous MIL-125 (Ti)[J]. ACS Applied Materials & Interfaces, 2015, 7(9): 5338-5346.
68	Hou C C, Wang Y, Zou L L, et al. A gas-steamed MOF route to P-doped open carbon cages with enhanced Zn-ion energy storage capability and ultrastability[J]. Advanced Materials, 2021, 33(31): e2101698.
69	Huang H L, Sun Y X, Jia X M, et al. Air-steam etched construction of hierarchically porous metal-organic frameworks[J]. Chinese Journal of Chemistry, 2021, 39(6): 1538-1544.
70	Chen Y, Dai Y H, Xiong Q Z, et al. Synthesis of hierarchically porous Cu-BTC through phase-controlled etching[J]. Chemical Engineering Science, 2024, 297: 120293.
71	代艳辉, 熊启钊, 房强, 等. 原位蒸汽辅助法用于一步制备多级孔Cu-BTC[J]. 化工学报, 2024, 75(9): 3329-3337.
	Dai Y H, Xiong Q Z, Fang Q, et al. In situ steam-assisted method for one-step synthesis of hierarchically porous Cu-BTC[J]. CIESC Journal, 2024, 75(9): 3329-3337.
72	Cohen S M. Postsynthetic methods for the functionalization of metal-organic frameworks[J]. Chemical Reviews, 2012, 112(2): 970-1000.
73	Liu L J, Li L, Ziebel M E, et al. Metal-diamidobenzoquinone frameworks via post-synthetic linker exchange[J]. Journal of the American Chemical Society, 2020, 142(10): 4705-4713.
74	Su P C, Tu M, Ameloot R, et al. Vapor-phase processing of metal-organic frameworks[J]. Accounts of Chemical Research, 2022, 55(2): 186-196.
75	Park K S, Ni Z, Côté A P, et al. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks[J]. Proceedings of the National Academy of Sciences of the United States of America, 2006, 103(27): 10186-10191.
76	Marreiros J, Van Dommelen L, Fleury G, et al. Vapor-phase linker exchange of the metal-organic framework ZIF-8: a solvent-free approach to post-synthetic modification[J]. Angewandte Chemie International Edition, 2019, 58(51): 18471-18475.
77	Wu W F, Su J Y, Jia M M, et al. Vapor-phase linker exchange of metal-organic frameworks[J]. Science Advances, 2020, 6(18): eaax7270.
78	Kim I S, Ahn S, Vermeulen N A, et al. The synthesis science of targeted vapor-phase metal-organic framework postmodification[J]. Journal of the American Chemical Society, 2020, 142(1): 242-250.
79	De S, Quan G C, Gikonyo B, et al. Vapor-phase infiltration inside a microporous porphyrinic metal-organic framework for postsynthesis modification[J]. Inorganic Chemistry, 2020, 59(14): 10129-10137.

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