Research on Zr-based metal-organic frameworks for NH3 adsorption

doi:10.11949/0438-1157.20220021

Abstract

Abstract:

Metal-organic framework (MOF) has been developed rapidly in the fields of gas adsorption and storage in recent years, but they are unsatisfactory in the adsorption of strong corrosive gas ammonia (NH₃) due to structural instability. Considering NH₃ is the only carbon-free chemical energy carrier, developing efficient ammonia storage technology to carry hydrogen is an effective technology to reduce carbon dioxide emissions. MOFs exhibit great prospects for adsorption and storage of NH₃ due to their high surface area and structural diversity advantages. NH₃ has a lone pair of electrons, which will attack the coordination bond formed between the metal ion and the ligand, resulting in the structural destruction of MOFs. Herein, the structural characteristics, stability, and NH₃ adsorption properties of Zr-based metal-organic frameworks, including UiO-66, NU-1000, MOF-801, and MOF-808, were investigated by experiments and computational simulations. The results showed that UiO-66 has excellent structural stability in NH₃ adsorption with a high uptake of 13.04, 6.38 and 9.65 mmol/g. However, Due to the limited stability and low adsorption capacity, NU-1000 and MOF-801 are not suitable for ammonia adsorption under the humid environment. Conversely, the structure of UiO-66 and MOF-808 is very stable, which can be used in NH₃ adsorption and storage applications both in dry and humid NH₃ environments.

Key words: metal-organic framework, Zr-based series, NH₃ adsorption, stability, cycling ability

摘要：

近年来，金属有机骨架材料（MOF）在气体吸附和储存领域得到了迅速发展，但由于结构的不稳定性，其在强腐蚀性气体氨（NH₃）的吸附方面并不令人满意。考虑到NH₃是唯一的无碳排放的氢能源载体，开发高效的储氨技术来载氢是有效的降低二氧化碳排放的手段。利用MOF材料具有的高比表面积和结构多样的特性，在NH₃的吸附和储存方面具有广阔的应用前景。而NH₃具有孤对电子，会攻击金属与配体之间形成的配位键，使MOF材料的结构遭到破坏。锆基金属有机骨架材料是公认结构稳定性较好的MOF材料，但其是否能胜任干燥NH₃及含水条件下的稳定性仍未深入考察，由此需探究该系列材料在NH₃吸附领域的适用性。在此，通过实验和计算模拟研究锆基系列的金属有机骨架UiO-66、NU-1000、MOF-801和 MOF-808的结构特征、稳定性和NH₃吸附性能。结果表明，UiO-66、NU-1000和MOF-808在纯NH₃环境下的稳定性较好，并且显示出高吸附量且可循环的氨吸附性能（13.04、6.38、9.65 mmol/g）。受限于水和氨对结构的协同破坏作用，NU-1000和MOF-801的结构均不能维持，而UiO-66和MOF-808的结构非常稳定，无论在干燥NH₃环境及含水NH₃环境下均能胜任而应用于NH₃吸附和储存。

关键词: 金属有机骨架材料, 锆基系列, 氨吸附, 稳定性, 循环性

CLC Number:

TQ 536.9

Yi WANG, Qizhao XIONG, Yang CHEN, Jiangfeng YANG, Libo LI, Jinping LI. Research on Zr-based metal-organic frameworks for NH₃ adsorption[J]. CIESC Journal, 2022, 73(4): 1772-1780.

王毅, 熊启钊, 陈杨, 杨江峰, 李立博, 李晋平. 锆基金属有机骨架材料用于氨吸附性能的研究[J]. 化工学报, 2022, 73(4): 1772-1780.

Figures/Tables 8

Fig.1 The structures of UiO-66, MOF-801 and MOF-808 with cages and NU-1000 with channels

Fig.2 SEM images of synthesized UiO-66, NU-1000, MOF-801, and MOF-808 and after NH3/H2O co-adsorption

Fig.3 PXRD patterns of UiO-66, NU-1000, MOF-801 and MOF-808

Fig.4 TGA curves of UiO-66, NU-1000, MOF-801 and MOF-808

Fig.5 N2 (77 K) ad/desorption isotherms of UiO-66, NU-1000, MOF-801 and MOF-808

Fig.6 Cycles NH3 ad/desorption curves of UiO-66, NU-1000, MOF-801 and MOF-808 at 25℃

Table 1 Pore structure and adsorption performance of the samples

材料	BET比表面积/(m²/g)	孔径/?	孔体积/(cm³/g)	298 K NH₃吸附量/(mmol/g)
UiO-66	916	8.4,7.4	0.49	13.04
NU-1000	1567	31	1.4	6.38
MOF-801	873	7.4,5.6,4.8	0.45	9.85
MOF-808	1512	4.8,18.4	0.84	9.65

Fig.7 The adsorbed NH3 molecule density (red points) in UiO-66, NU-1000, MOF-801 and MOF-808 obtained from the GCMC simulations at 1 bar and 25℃

References 45

1	Li K, Andersen S Z, Statt M J, et al. Enhancement of lithium-mediated ammonia synthesis by addition of oxygen[J]. Science, 2021, 374(6575): 1593-1597.
2	Zhang Y Y, Zhang X, Chen Z J, et al. A flexible interpenetrated zirconium-based metal-organic framework with high affinity toward ammonia[J]. ChemSusChem, 2020, 13(7): 1710-1714.
3	MacFarlane D R, Choi J, Suryanto B H, et al. Liquefied sunshine: transforming renewables into fertilizers and energy carriers with electromaterials[J]. Advanced Materials, 2020, 32(18): e1904804.
4	MacFarlane D R, Cherepanov P V, Choi J, et al. A roadmap to the ammonia economy[J]. Joule, 2020, 4(6): 1186-1205.
5	Guo J P, Chen P. Catalyst: NH₃ as an energy carrier[J]. Chem, 2017, 3(5): 709-712.
6	Chen Y, Zhang F, Wang Y, et al. Recyclable ammonia uptake of a MIL series of metal-organic frameworks with high structural stability[J]. Microporous and Mesoporous Materials, 2018, 258: 170-177.
7	Zhao Y, Setzler B P, Wang J, et al. An efficient direct ammonia fuel cell for affordable carbon-neutral transportation[J]. Joule, 2019, 3(10): 2472-2484
8	王均利, 曾少娟, 陈能, 等. 氨气吸附材料的研究进展[J]. 过程工程学报, 2019, 19(1): 14-24.
	Wang J L, Zeng S J, Chen N, et al. Research progress of ammonia adsorption materials[J]. The Chinese Journal of Process Engineering, 2019, 19(1): 14-24.
9	金青青, 梁晓怿, 张佳楠, 等. 改性球形活性炭对氨气吸附性能的研究[J]. 无机盐工业, 2021, 53(4): 61-66.
	Jin Q Q, Liang X Y, Zhang J N, et al. Study on adsorption performance of modified spherical activated carbon for ammonia[J]. Inorganic Chemicals Industry, 2021, 53(4): 61-66.
10	杨江峰, 欧阳坤, 陈杨, 等. 柔性MOFs材料Cu(BDC)的氨气吸附及可逆转化性能[J]. 化工学报, 2017, 68(1): 418-423.
	Yang J F, Ouyang K, Chen Y, et al. NH₃ adsorption on flexy reversible metal-organic frameworks Cu(BDC)[J]. CIESC Journal, 2017, 68(1): 418-423.
11	Sharonov V E, Aristov Y I. Ammonia adsorption by MgCl₂, CaCl₂ and BaCl₂ confined to porous alumina: the fixed bed adsorber[J]. Reaction Kinetics and Catalysis Letters, 2005, 85(1): 183-188.
12	Helminen J, Helenius J, Paatero E, et al. Adsorption equilibria of ammonia gas on inorganic and organic sorbents at 298.15 K[J]. Journal of Chemical & Engineering Data, 2001, 46(2): 391-399.
13	Furukawa H, Ko N, Go Y B, et al. Ultrahigh porosity in metal-organic frameworks[J]. Science, 2010, 329(5990): 424-428.
14	Farha O K, Eryazici I, Jeong N C, et al. Metal-organic framework materials with ultrahigh surface areas: is the sky the limit? [J]. Journal of the American Chemical Society, 2012, 134(36): 15016-15021.
15	Li J R, Kuppler R J, Zhou H C. Selective gas adsorption and separation in metal-organic frameworks[J]. Chemical Society Reviews, 2009, 38(5): 1477-1504.
16	Chen Y, Xiong Q Z, Wang Y, et al. Boosting molecular recognition of acetylene in UiO-66 framework through pore environment functionalization[J]. Chemical Engineering Science, 2021, 237:116572
17	Zhou H C, Long J R, Yaghi O M. Introduction to metal-organic frameworks[J]. Chemical Reviews, 2012, 112(2): 673-674.
18	Zhou H C J, Kitagawa S. Metal-organic frameworks (MOFs)[J]. Chemical Society Reviews, 2014, 43(16): 5415-5418.
19	Furukawa H, Cordova K E, O'Keeffe M, et al. The chemistry and applications of metal-organic frameworks[J]. Science, 2013, 341(6149):1230444.
20	Li J R, Sculley J, Zhou H C. Metal-organic frameworks for separations[J]. Chemical Reviews, 2012, 112(2): 869-932.
21	Cui Y J, Yue Y F, Qian G D, et al. Luminescent functional metal-organic frameworks[J]. Chemical Reviews, 2012, 112(2): 1126-1162.
22	Li L B, Lin R-B, Krishna R, et al. Ethane/ethylene separation in a metal-organic framework with iron-peroxo sites[J]. Science, 2018, 362(6413): 443-446.
23	Travlou N A, Singh K, Rodríguez-Castellón E, et al. Cu-BTC MOF-graphene-based hybrid materials as low concentration ammonia sensors[J]. Journal of Materials Chemistry A, 2015, 3(21): 11417-11429.
24	Britt D, Tranchemontagne D, Yaghi O M. Metal-organic frameworks with high capacity and selectivity for harmful gases[J]. Proceedings of the National Academy of Sciences of the United States of America, 2008, 105(33): 11623-11627.
25	Doonan C J, Tranchemontagne D J, Glover T G, et al. Exceptional ammonia uptake by a covalent organic framework[J]. Nature Chemistry, 2010, 2(3): 235-238.
26	Glover T G, Peterson G W, Schindler B J, et al. MOF-74 building unit has a direct impact on toxic gas adsorption[J]. Chemical Engineering Science, 2011, 66(2): 163-170.
27	Petit C, Bandosz T J. Enhanced adsorption of ammonia on metal-organic framework/graphite oxide composites: analysis of surface interactions[J]. Advanced Functional Materials, 2010, 20(1): 111-118.
28	Petit C, Mendoza B, Bandosz T J. Reactive adsorption of ammonia on Cu-based MOF/graphene composites[J]. Langmuir, 2010, 26(19): 15302-15309.
29	Petit C, Bandosz T J. Synthesis, characterization, and ammonia adsorption properties of mesoporous metal–organic framework (MIL(Fe))-graphite oxide composites: exploring the limits of materials fabrication[J]. Advanced Functional Materials, 2011, 21(11): 2108-2117.
30	Bai Y, Dou Y B, Xie L H, et al. Zr-based metal-organic frameworks: design, synthesis, structure, and applications[J]. Chemical Society Reviews, 2016, 45(8): 2327-2367.
31	Cavka J H, Jakobsen S, Olsbye U, et al. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability[J]. Journal of the American Chemical Society, 2008, 130(42): 13850-13851.
32	Deria P, Mondloch J E, Tylianakis E, et al. Perfluoroalkane functionalization of NU-1000 via solvent-assisted ligand incorporation: synthesis and CO₂ adsorption studies[J]. Journal of the American Chemical Society, 2013, 135(45): 16801-16804.
33	Furukawa H, Gándara F, Zhang Y B, et al. Water adsorption in porous metal-organic frameworks and related materials[J]. Journal of the American Chemical Society, 2014, 136(11): 4369-4381.
34	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.
35	Gelb L D, Gubbins K E. Characterization of porous glasses: simulation models, adsorption isotherms, and the Brunauer- Emmett-Teller analysis method[J]. Langmuir, 1998, 14(8): 2097-2111.
36	Chen Y, Wang Y, Yang C Y, et al. Antenna-protected metal-organic squares for water/ammonia uptake with excellent stability and regenerability[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(6): 5082-5089.
37	Liu Y, Liu J, Lin Y S, et al. Effects of water vapor and trace gas impurities in flue gas on CO₂/N₂ separation using ZIF-68[J]. The Journal of Physical Chemistry C, 2014, 118(13): 6744-6751.
38	Moghadam P Z, Ghosh P, Snurr R Q. Understanding the effects of preadsorbed perfluoroalkanes on the adsorption of water and ammonia in MOFs[J]. The Journal of Physical Chemistry C, 2015, 119(6): 3163-3170.
39	Nijem N, Fürsich K, Bluhm H, et al. Ammonia adsorption and co-adsorption with water in HKUST-1: spectroscopic evidence for cooperative interactions[J]. The Journal of Physical Chemistry C, 2015, 119(44): 24781-24788.
40	Huang C C, Li H S, Chen C H. Effect of surface acidic oxides of activated carbon on adsorption of ammonia[J]. Journal of Hazardous Materials, 2008, 159(2/3): 523-527.
41	Saha D, Deng S G. Ammonia adsorption and its effects on framework stability of MOF-5 and MOF-177[J]. Journal of Colloid and Interface Science, 2010, 348(2): 615-620.
42	Kajiwara T, Higuchi M, Watanabe D, et al. A systematic study on the stability of porous coordination polymers against ammonia[J]. Chemistry-A European Journal, 2014, 20(47): 15611-15617.
43	Petit C, Huang L L, Jagiello J, et al. Toward understanding reactive adsorption of ammonia on Cu-MOF/graphite oxide nanocomposites[J]. Langmuir, 2011, 27(21): 13043-13051.
44	Rieth A J, Tulchinsky Y, Dincă M. High and reversible ammonia uptake in mesoporous azolate metal-organic frameworks with open Mn, Co, and Ni sites[J]. Journal of the American Chemical Society, 2016, 138(30): 9401-9404.
45	Han X, Lu W P, Chen Y L, et al. High ammonia adsorption in mfm-300 materials: dynamics and charge transfer in host-guest binding[J]. Journal of the American Chemical Society, 2021, 143(8): 3153-3161.

[1]	He JIANG, Junfei YUAN, Lin WANG, Guyu XING. Experimental study on the effect of flow sharing cavity structure on phase change flow characteristics in microchannels [J]. CIESC Journal, 2023, 74(S1): 235-244.
[2]	Lingding MENG, Ruqing CHONG, Feixue SUN, Zihui MENG, Wenfang LIU. Immobilization of carbonic anhydrase on modified polyethylene membrane and silica [J]. CIESC Journal, 2023, 74(8): 3472-3484.
[3]	Yuyuan ZHENG, Zhiwei GE, Xiangyu HAN, Liang WANG, Haisheng CHEN. Progress and prospect of medium and high temperature thermochemical energy storage of calcium-based materials [J]. CIESC Journal, 2023, 74(8): 3171-3192.
[4]	Bin CAI, Xiaolin ZHANG, Qian LUO, Jiangtao DANG, Liyuan ZUO, Xinmei LIU. Research progress of conductive thin film materials [J]. CIESC Journal, 2023, 74(6): 2308-2321.
[5]	Lei MAO, Guanzhang LIU, Hang YUAN, Guangya ZHANG. Efficient preparation of carbon anhydrase nanoparticles capable of capturing CO₂ and their characteristics [J]. CIESC Journal, 2023, 74(6): 2589-2598.
[6]	Wenchao XU, Zhigao SUN, Cuimin LI, Juan LI, Haifeng HUANG. Effect of surfactant E-1310 on the formation of HCFC-141b hydrate under static conditions [J]. CIESC Journal, 2023, 74(5): 2179-2185.
[7]	Zijian WANG, Ming KE, Jiahan LI, Shuting LI, Jinru SUN, Yanbing TONG, Zhiping ZHAO, Jiaying LIU, Lu REN. Progress in preparation and application of short b-axis ZSM-5 molecular sieve [J]. CIESC Journal, 2023, 74(4): 1457-1473.
[8]	Runzhu LIU, Tiantian CHU, Xiaoa ZHANG, Chengzhong WANG, Junying ZHANG. Synthesis and properties of phenylene-containing α,ω-hydroxy-terminated fluorosilicone polymers [J]. CIESC Journal, 2023, 74(3): 1360-1369.
[9]	Xiangshang CHEN, Zhenjie MA, Xihua REN, Yue JIA, Xiaolong LYU, Huayan CHEN. Preparation and mass transfer efficiency of three-dimensional network extraction membrane [J]. CIESC Journal, 2023, 74(3): 1126-1133.
[10]	Guojun XI, Zihan LIU, Guangping LEI. Enhanced adsorption and separation of low concentration coalbed methane based on synergistic effect between FeTPPs and CuBTC [J]. CIESC Journal, 2022, 73(9): 3940-3949.
[11]	Hongxin YANG, Xingya LI, Liang GE, Tongwen XU. Preparation of mono-/divalent anion permselective membranes with piperidinium-type long side-chain [J]. CIESC Journal, 2022, 73(8): 3739-3748.
[12]	Jiangwei ZHU, Pengfei MA, Xiao DU, Yanyan YANG, Xiaogang HAO, Shanxia LUO. Specific electronically controlled separation of phosphate anions based on variable valence NiFe-LDH/rGO [J]. CIESC Journal, 2022, 73(7): 3057-3067.
[13]	Xue’an LIU, Liyi TANG, Jian QIN, Dajiang TANG, Zhangfa TONG, Huiying QU. Preparation of carbon nanotube bridged porous carbon by Ni/Co-ZIF-8 pyrolysis and its application to supercapacitors [J]. CIESC Journal, 2022, 73(7): 3287-3297.
[14]	Jianfei SONG, Liqiang SUN, Ming XIE, Yaodong WEI. Experimental study of instability of gas-phase swirling flow in cyclone [J]. CIESC Journal, 2022, 73(7): 2858-2864.
[15]	Ke XU, Guoqiang SHI, Dongfeng XUE. Inorganic hybrid perovskite cluster materials: luminescence properties of mesoscale perovskite materials [J]. CIESC Journal, 2022, 73(6): 2748-2756.

Research on Zr-based metal-organic frameworks for NH₃ adsorption

锆基金属有机骨架材料用于氨吸附性能的研究

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 8

References 45

Related Articles 15

Recommended Articles

Metrics

Comments