石墨烯量子点辅助合成Cu-MOFs及CO<sub>2</sub>吸附行为

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摘要选用一种成本低、可大规模合成的Cu基MOFs（Cu-MOFs）材料作为CO₂吸附剂，在原位合成过程中添加石墨烯量子点以调控其晶体结构.结果表明：适量石墨烯量子点的添加有利于提高Cu-MOFs的比表面积和孔体积，相比未改性MOFs材料，改性后的CO₂吸附性能有所提高，25℃，100kPa时提高了4.5%.随着温度升高，吸附容量提升越明显.改性后的MOFs对于N₂的吸附量则比未改性时更低，因此计算得到的CO₂/N₂吸附选择性也更高，增加了近一倍.综合等量吸附热的考察结果发现，尤其添加适量含N石墨烯量子点的Cu-MOFs吸附剂不仅具备了较高的吸附容量、吸附选择性，还展现了较理想的吸附热，因此兼具了较优CO₂吸附性能和较低脱附能耗的特点，为MOFs吸附剂的改性提供了一点参考价值.

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	庞米杰
	陈钰文
	王婉慈
	赵云霞

关键词 ：金属有机框架MOFs, 石墨烯量子点, CO₂吸附, 吸附选择性, 吸附热

Abstract：In this paper, a kind of Cu-based MOFs which is low-cost and easy to be synthesized in large-scale was selected as the CO₂ adsorbent. Graphene quantum dots (GQDs) were in-situ incorporated in the synthesis process of MOFs to control their crystal structure. The research results indicated that adding of a proper amount of GQDs was beneficial to increase the specific surface area and pore volume of Cu-MOFs. Compared with the pristine MOFs, CO₂ adsorption capacities of the modified MOFs were improved. At 25℃ and 100kPa, the highest increased 4.5%. As temperature increased, the improvement of CO₂ adsorption capacity was more obvious. The adsorption capacities of the modified MOFs for N₂ were lower than that of the pristine MOFs, thus their calculated adsorption selectivity values of CO₂/N₂ were higher and nearly doubled. Combined with the results of isosteric heats of CO₂ adsorption, especially the Cu-MOFs adsorbent added with a proper amount of N-doped graphene quantum dots, which not only had higher CO₂ uptake and selectivity, but exhibited more ideal adsorption heat within the physical adsorption category. Therefore, it has the characteristics of superior CO₂ adsorption performance and low energy consumption for desorption, which provides a little reference value for the modification of MOFs adsorbent.

Key words： metal-organic frameworks (MOFs) graphene quantum dots (GQDs) CO₂ adsorption adsorption selectivity adsorption heat

收稿日期: 2021-02-05

PACS:

X511

基金资助:国家自然科学基金资助项目（51802160）；南京信息工程大学大学生实践创新训练计划项目（202010300137）

通讯作者: 赵云霞,副教授,nlgzyx@nuist.edu.cn E-mail: nlgzyx@nuist.edu.cn

作者简介: 庞米杰(1999-),男,浙江台州人,南京信息工程大学本科生,主要从事二氧化碳吸附方面的研究.

引用本文:

庞米杰, 陈钰文, 王婉慈, 赵云霞. 石墨烯量子点辅助合成Cu-MOFs及CO₂吸附行为[J]. 中国环境科学, 2021, 41(10): 4565-4571. PANG Mi-jie, CHEN Yu-wen, WANG Wan-ci, ZHAO Yun-xia. Synthesis and CO₂ adsorptive storage of Cu-MOFs by graphene quantum dots-assistant route. CHINA ENVIRONMENTAL SCIENCECE, 2021, 41(10): 4565-4571.

链接本文:

http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2021/V41/I10/4565

[1]	Zhang G J, ZhaoP Y, Hao L X, et al. Amine-modiﬁed SBA-15(P):A promising adsorbent for CO2 capture[J]. Journal of CO2 Utilization, 2018,24:22-33.
[2]	Zhang Z J, Huang S S, Xian S K, et al. Adsorption equilibrium and kinetics of CO2 on chromium terephthalate MIL-101[J]. Energy Fuels, 2011,25:835-842.
[3]	骆仲泱,方梦祥,李明远,等.二氧化碳捕集封存和利用技术[M]. 北京:中国电力出版社, 2012:15-16.Luo Z Y, Fang M X, Li M Y, et al. Carbon dioxide capture, storage and utilization technology[M]. Beijing:CEPP, 2012:15-16.
[4]	Seoane B, Castellanos S, Dikhtia Renko A, et al. Multiscale crystal engineering of metal organic frameworks[J]. Coordination Chemistry Reviews, 2016,307(2):147-187.
[5]	Yazaydin A O, Benin A I, Faheem S A, et al. Enhanced CO2 adsorption in metal-organic frameworks via occupation of open-metal sites by coordinated water molecules[J]. Chemistry of Materials, 2009,21:1425-1430.
[6]	Landaverde-Alvarado C, Morris A J, Martin S M. Gas sorption and kinetics of CO2 sorption and transport in a polymorphic microporous MOF with open Zn (II) coordination sites[J]. Journal of CO2 Utilization, 2017,19:40-48.
[7]	张秀芳,安晓辉,刘大欢,等.离子交换对usf-ZMOF二氧化碳吸附能力影响的研究[J]. 化学学报, 2011,69(1):84-88.Zhang X F, An X H, Liu D H, et al. Study of the influence of ion-exchange on carbon dioxide adsorption capacity in usf-ZMOF[J]. Journal of Chemistry, 2011,69(1):84-88.
[8]	Zhou Z, Mei L, Ma C, et al. A novel bimetallic MIL-101(Cr, Mg) with high CO2 adsorption capacity and CO2/N2 selectivity[J]. Chemical Engineering Science, 2016,147:109-117.
[9]	Su X, Bromberg L, Hatton T A, et al. Postsynthetic functionalization of Mg-MOF-74 with tetraethylenepentamine:Structural characterization and enhanced CO2 adsorption[J]. ACS Applied Materials & Interfaces, 2017,9(12):11299-11306.
[10]	Liu S, Sun L, Xu F, et al. Nanosized Cu-MOFs induced by graphene oxide and enhanced gas storage capacity[J]. Energy & Environmental Science, 2013,6:818-823.
[11]	Xu G Y, Yuan J R, Geng X M, et al. Caterpillar-like graphene confining sulfur by restacking effect for high performance lithium sulfur batteries[J]. Chemical Engineering Journal, 2017,322:454-462.
[12]	Weng H, Yan B. N-GQDs and Eu3+ co-encapsulated anionic MOFs:Two-dimensional luminescent platform for decoding benzene homologues[J]. Dalton Transactions, 2016,45:8795-8801.
[13]	Li F, Duan C, Zhang H, et al. Hierarchically porous metal-organic frameworks:green synthesis and high space-time yield[J]. Industrial & Engineering Chemistry Research, 2018,57(28):9136-9143.
[14]	Mckinstry C, Cussen E J, Fletcher A J, et al. Scalable continuous production of high quality HKUST-1via conventional and microwave heating[J]. Chemical Engineering Journal, 2017,326:570-577.
[15]	石勇,牛丹阳,武卓敏,等.Ag/Cu3(BTC)2复合催化剂的制备及其NH3-SCR催化性能[J]. 中国环境科学, 2018,38(7):2445-2450.Shi Y, Niu D Y, Wu Z M, et al. Synthesis of Ag/Cu3(BTC)2 composite catalysts and their catalytic performance for NH3-SCR[J]. China Environmental Science, 2018,38(7):2445-2450.
[16]	Dong Y, Shao J, Chen C, et al. Blue luminescent graphene quantum dots and graphene oxide prepared by tuning the carbonization degree of citric acid[J]. Carbon, 2012,50:4738-4743.
[17]	马庆运,张纪梅,张坤,等.热解柠檬酸制备石墨烯量子点及其光学性质研究[J]. 化工新型材料, 2017,45(2):70-72.Ma Q Y, Zhang J M, Zhang K, et al. Citrate pyrolysis and synthesis of graphene quantum dots and study on optical property[J]. New chemical materials, 2017,45(2):70-72.
[18]	Qu D, Zheng M, Zhang L, et al. Formation mechanism and optimization of highly luminescent N-doped graphene quantum dots[J]. Scientific Reports, 2014,4:5294.
[19]	Chui S Y, Lo M F, Charmant J P H, et al. A chemically functionalizable nanoporous material[Cu3(TMA)2(H2O)3]n[J]. Science, 1999,283:1148-1150.
[20]	Sumida K, Rogow D L, Long J R, et al. Carbon dioxide capture in metal organic frameworks[J]. Chemical Reviews, 2012,112:724-781.
[21]	Huang W, Zhou X, Xia Q, et al. Preparation and adsorption performance of GrO@Cu-BTC for separation of CO2/CH4[J]. Industrial & Engineering Chemistry Research, 2014,53(27):11176-11184.
[22]	Yoo D K, Yoon T-U, Bae Y-S, et al. Metal-organic framework MIL-101loaded with polymethacrylamide with or without further reduction:Effective and selective CO2 adsorption with amino or amide functionality[J]. Chemical Engineering Journal, 2020,380:122496.
[23]	Xian S, Li X, Xu F, et al. Adsorption isotherms, kinetics, and desorption of 1,2-dichloroethane on chromium-based metal organic framework MIL-101[J]. Separation Science and Technology, 2013, 48(10):1479-1489.
[24]	Chen Y, Lv D, Wu J, et al. A new MOF-505@GO composite with high selectivity for CO2/CH4 and CO2/N2 separation[J]. Chemical Engineering Journal, 2017,308:1065-1072.
[25]	Rao L, Liu S, Wang L, et al. N-doped porous carbons from low-temperature and single-step sodium amide activation of carbonized water chestnut shell with excellent CO2 capture performance[J]. Chemical Engineering Journal, 2019,359:428-435.
[26]	Park J M, Yoo D K, Jhung S H. Selective CO2 adsorption over functionalized Zr-based metal organic framework under atmospheric or lower pressure:Contribution of functional groups to adsorption[J]. Chemical Engineering Journal, 2020,402:126254.