基于UiO-66骨架的氧化石墨烯改性金属有机框架凝胶的制备及其对甲苯的高效吸附性能

doi:10.15541/jim20250265

无机材料学报 ›› 2026, Vol. 41 ›› Issue (4): 519-526.DOI: 10.15541/jim20250265 CSTR: 32189.14.10.15541/jim20250265

所属专题：【能源环境】金属有机框架材料MOF(202512)

基于UiO-66骨架的氧化石墨烯改性金属有机框架凝胶的制备及其对甲苯的高效吸附性能

朱开煌¹^,²(), 杨世杰²^,³, 李欣格²^,³, 宋贯卿²^,³, 史淦升², 王焱², 任小孟⁴, 陆遥¹, 徐新宏⁴(), 孙静²()

¹ 沈阳化工大学材料科学与工程学院, 沈阳 110142
² 中国科学院上海硅酸盐研究所, 关键陶瓷材料全国重点实验室, 上海 201899
³ 中国科学院大学, 北京 100049
⁴ 中国人民解放军海军特色医学中心, 上海 200433

收稿日期:2025-06-23 修回日期:2025-09-04 出版日期:2025-09-11 网络出版日期:2025-09-11
通讯作者: 孙静, 研究员. E-mail: jingsun@mail.sic.ac.cn;
徐新宏, 助理研究员. E-mail: xxh2748@163.com
作者简介:朱开煌(2000-), 男, 硕士研究生. E-mail: ZHUkaihuang_11@outlook.com

Graphene Oxide Modified UiO-66 Based Metal Organic Framework Gel: Preparation and Efficient Toluene Adsorption Performance

ZHU Kaihuang¹^,²(), YANG Shijie²^,³, LI Xinge²^,³, SONG Guanqing²^,³, SHI Gansheng², WANG Yan², REN Xiaomeng⁴, LU Yao¹, XU Xinhong⁴(), SUN Jing²()

¹ College of Materials Science and Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China
² State Key Laboratory of High Performance Ceramics, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China
³ University of Chinese Academy of Sciences, Beijing 100049, China
⁴ Navy Medical Centre, Shanghai 200433, China

Received:2025-06-23 Revised:2025-09-04 Published:2025-09-11 Online:2025-09-11
Contact: SUN Jing, professor. E-mail: jingsun@mail.sic.ac.cn;
XU Xinhong, assistant professor. E-mail: xxh2748@163.com
About author:ZHU Kaihuang (2000-), male, Master candidate. E-mail: ZHUkaihuang_11@outlook.com

摘要/Abstract

摘要：

挥发性有机化合物(VOCs), 尤其是芳香烃类物质如甲苯, 由于其高挥发性和生物毒性, 严重威胁环境与人类健康。传统的金属有机框架(MOFs)材料多以微孔结构为主, 但在吸附容量与分子传质之间存在矛盾, 这促使研究者探索更优的材料体系。本研究以UiO-66为主体, 复合氧化石墨烯(GO)进行改性, 构建了GO复合的金属有机框架凝胶(MOGs)。GO的π共轭结构增强了与甲苯分子的π-π相互作用, 丰富的含氧官能团则促进了与金属节点的配位, 形成更多Lewis酸性位点, 协同增强了金属-π相互作用。实验结果显示, UG-1样品(GO与ZrCl₄质量比为1 : 100)在动态穿透实验中的平衡吸附容量达77.4 mg/g, 静态吸附实验中的饱和吸附容量高达1245.5 mg/g, 优于UiO66 MOF和UiO66 MOG, 表现出卓越的吸附性能。本工作揭示了GO改性对材料孔结构及主-客体相互作用的多重调控机理, 为设计高效可再生VOCs吸附剂提供了新的理论基础和实践支撑。

关键词: 氧化石墨烯, 金属有机框架, 挥发性有机化合物, 多级孔结构

Abstract:

Volatile organic compounds (VOCs), particularly aromatic hydrocarbons such as toluene, pose significant threats to the environment and human health due to their high volatility and biological toxicity. Traditional metal- organic frameworks (MOFs) are primarily microporous, and their trade-off between adsorption capacity and molecular transport efficiency has driven development of more advanced material systems. In this work, graphene oxide (GO) doped metal-organic framework gels (MOGs) based on UiO-66 were developed, leveraging the synergistic modification effect of GO. The π-conjugated structure of GO enhanced π-π interactions with toluene molecules, while its abundant oxygen-containing functional groups facilitated competitive coordination with metal nodes, leading to exposure of additional Lewis acid sites and thereby enhancing metal-π interactions. Experimental results demonstrated that UG-1 with a mass ratio of GO to ZrCl₄ at 1 : 100 exhibited a breakthrough adsorption capacity of 77.4 mg/g in dynamic adsorption experiments and a saturated capacity of up to 1245.5 mg/g in static tests, outperforming both UiO66 MOF and UiO66 MOG materials. In conclusion, this study elucidates multiple regulatory mechanisms of GO incorporation in modulating pore structure and host-guest interactions, providing a new theoretical basis and practical guidance for designing efficient and recyclable VOC adsorbents.

Key words: graphene oxide, metal-organic framework, volatile organic compound, hierarchical pore structure

中图分类号:

TQ174

朱开煌, 杨世杰, 李欣格, 宋贯卿, 史淦升, 王焱, 任小孟, 陆遥, 徐新宏, 孙静. 基于UiO-66骨架的氧化石墨烯改性金属有机框架凝胶的制备及其对甲苯的高效吸附性能[J]. 无机材料学报, 2026, 41(4): 519-526.

ZHU Kaihuang, YANG Shijie, LI Xinge, SONG Guanqing, SHI Gansheng, WANG Yan, REN Xiaomeng, LU Yao, XU Xinhong, SUN Jing. Graphene Oxide Modified UiO-66 Based Metal Organic Framework Gel: Preparation and Efficient Toluene Adsorption Performance[J]. Journal of Inorganic Materials, 2026, 41(4): 519-526.

图/表 11

图1 甲苯动态穿透吸附实验的流程示意图

Fig. 1 Experiment flow diagram of the toluene breakthrough adsorption

图2 UiO66 MOF、UiO66 MOG、UG-1和UG-2的(a) XRD图谱和(b)拉曼光谱

Fig. 2 (a) XRD patterns and (b) Raman spectra of UiO66 MOF, UiO66 MOG, UG-1, and UG-2

图3 UiO66 MOF、UiO66 MOG、UG-1和UG-2的(a) N2吸-脱附等温曲线、(b) 0~10 nm的孔径分布图(插图为0.5~3 nm的孔径放大图)和(c) 10~30 nm的孔径分布图

Fig. 3 (a) N2 adsorption-desorption isotherms, and pore size distribution curves in the ranges of (b) 0-10 nm and (c) 10-30 nm of UiO66 MOF, UiO66 MOG, UG-1, and UG-2 with inset in (b) showing magnified view for the 0.5-3 nm range

表1 UiO66 MOF、UiO66 MOG和UG-x的比表面积以及孔结构参数

Table 1 Specific surface area and pore structure parameters of UiO66 MOF, UiO66 MOG and UG-x

Sample	S_BET/(m²·g^-1)	S_micro/(m²·g^-1)	S_meso/(m²·g^-1)
UiO66 MOF	1020.9	945.2	75.7
UiO66 MOG	909.8	511.1	398.7
UG-1	973.8	536.8	437.0
UG-2	1062.4	749.5	312.9

图4 UiO66 MOF、UiO66 MOG、UG-1和UG-2的(a)甲苯静态吸附曲线(插图是吸附剂在低相对压力区间p/p0=0~0.05的甲苯静态吸附曲线)和(b)甲苯饱和吸附容量

Fig. 4 (a) Toluene vapor adsorption isotherms and (b) saturated toluene adsorption capacities of UiO66 MOF, UiO66 MOG, UG-1, and UG-2 with inset in (a) showing adsorption isotherms in a low-pressure region p/p0=0-0.05

表2 不同吸附剂的甲苯饱和吸附容量[2,18 -22]

Table 2 Toluene saturation adsorption capacities of various adsorbents[2,18 -22]

Adsorbent	p/p₀	Temperature/K	q/(mg·g^-1)
AC^[18]	1.0	298	530.4
Silica gel^[18]	1.0	298	437.4
UiO-66-NH₂@ABP^[19]	0.9	298	178.9
MIL-125-NH₂^[2]	0.94	298	293
MIL-100(Fe)_A2^[20]	1.0	298	523.3
HKUST-1^[21]	0.9	298	516
MSN-100^[22]	0.94	298	461
UG-1	1.0	298	1245.5

图5 UiO66 MOF、UiO66 MOG、UG-1 (a) 800和(b) 250 min内的甲苯动态穿透曲线和(c)甲苯平衡吸附容量

Fig. 5 Dynamic breakthrough curves for toluene adsorption within (a) 800 and (b) 250 min, and (c) equilibrium toluene adsorption capacities of UiO66 MOF, UiO66 MOG and UG-1

表3 UiO66 MOF、UiO66 MOG和UG-1的突破时间、平衡时间以及平衡吸附量

Table 3 Breakthrough time, equilibrium time and equilibrium adsorption capacities of UiO66 MOF, UiO66 MOG and UG-1

Sample	t_b/min	t_e/min	q/(mg·g^-1)
UiO66 MOF	200	580	59.7
UiO66 MOG	200	590	53.2
UG-1	240	750	77.4

图6 UiO66 MOF、UiO66 MOG和UG-1的甲苯TPD曲线

Fig. 6 TPD curves of toluene for UiO66 MOF, UiO66 MOG and UG-1

图7 (a) UiO66 MOG和(b) UG-1对甲苯吸附的原位DRIFTS图谱

Fig. 7 In-situ DRIFTS spectra of toluene adsorption for (a) UiO66 MOG and (b) UG-1 Colorful figures are available on website

图8 UiO66 MOG和UG-1的NH3-TPD曲线

Fig. 8 NH3-TPD curves of UiO66 MOG and UG-1

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基于UiO-66骨架的氧化石墨烯改性金属有机框架凝胶的制备及其对甲苯的高效吸附性能

Graphene Oxide Modified UiO-66 Based Metal Organic Framework Gel: Preparation and Efficient Toluene Adsorption Performance

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