Cu/Mg比对Cu/Mg-MOF-74的CO2吸附性能的影响

doi:10.15541/jim20230224

无机材料学报 ›› 2023, Vol. 38 ›› Issue (12): 1379-1386.DOI: 10.15541/jim20230224

所属专题：【能源环境】CO2绿色转换(202312)

Cu/Mg比对Cu/Mg-MOF-74的CO₂吸附性能的影响

凌洁¹^,²(), 周安宁¹(), 王文珍³(), 贾忻宇¹, 马梦丹¹

1.西安科技大学化学与化工学院, 西安 710054
2.陕西能源职业技术学院煤炭与化工产业学院, 咸阳 712000
3.西安石油大学化学化工学院, 西安 710065

收稿日期:2023-05-10 修回日期:2023-07-18 出版日期:2023-08-21 网络出版日期:2023-08-21
通讯作者: 周安宁, 教授. E-mail: psu564@139.com;
王文珍, 教授. E-mail: wzwang@xsyu.edu.cn
作者简介:凌洁(1984-), 女, 博士研究生. E-mail: 18629375447@163.com
基金资助:
国家自然科学基金(51674194);陕西高校青年杰出人才支持计划;陕西省自然科学基础研究计划(2021JQ-886)

Effect of Cu/Mg Ratio on CO₂ Adsorption Performance of Cu/Mg-MOF-74

LING Jie¹^,²(), ZHOU Anning¹(), WANG Wenzhen³(), JIA Xinyu¹, MA Mengdan¹

1. College of Chemistry & Chemical Engineering, Xi’an University of Science and Technology, Xi’an 710054, China
2. College of Coal & Chemical Industry, Shaanxi Energy Institute, Xianyang 712000, China
3. College of Chemistry & Chemical Engineering, Xi’an Shiyou University, Xi’an 710065, China

Received:2023-05-10 Revised:2023-07-18 Published:2023-08-21 Online:2023-08-21
Contact: ZHOU Anning, professor. E-mail: psu564@139.com;
WANG Wenzhen, professor. E-mail: wzwang@xsyu.edu.cn
About author:LING Jie (1984-), female, PhD candidate. E-mail: 18629375447@163.com
Supported by:
National Natural Science Foundation of China(51674194);Youth Talents Support Plan of Shaanxi;Natural Science Basic Research Program of Shaanxi(2021JQ-886)

摘要/Abstract

摘要：

Cu/Mg-MOF-74具有比表面积高、微孔结构和碱金属活性位点可调、CO₂吸附性能及光催化活性优良等优点, 但其Cu与Mg物质的量比(简称: Cu/Mg比)对烟气中CO₂吸附选择性影响机制尚不清晰。本研究采用溶剂热法合成了不同Cu/Mg比的Cu/Mg-MOF-74, 表征了其CO₂光催化性能、CO₂和N₂吸附量及孔结构, 计算了Cu/Mg-MOF-74的CO₂吸附选择性, 并分析了Cu/Mg比对吸附量、选择性影响机制。结果表明：随着Cu/Mg比减小, Cu/Mg-MOF-74光催化CO₂还原为CO和H₂的活性先增后减, 当Cu/Mg比为0.6/0.4时, 其光催化还原CO和H₂产率最大, 分别为10.65和5.41 μmol·h⁻¹·g_cat⁻¹(1 MPa, 150 ℃); 随着Cu/Mg比减小, CO₂、N₂在Cu/Mg-MOF-74上的吸附量增加, 且CO₂吸附量增加显著, 当Cu/Mg比为0.1/0.9时, 其CO₂、N₂吸附量最大, 分别为9.21、1.49 mmol·g⁻¹(273.15 K, 100 kPa); 随着Cu/Mg比减小, Cu/Mg-MOF-74的微孔(d₁≥0.7 nm)、超微孔(d₂<0.7 nm)的面积、体积均增加, 当Cu/Mg比为0.22/0.78时, 其微孔、超微孔的面积、体积均大于Mg-MOF-74; 其选择性随Cu/Mg比减小和CO₂浓度增大而改善。CO₂在Cu/Mg-MOF-74上的吸附作用包括微孔填充和Mg²⁺化学吸附, 微孔体积是影响其吸附性能的关键。调整Cu/Mg比可调控Cu/Mg-MOF-74的孔结构、CO₂吸附量和选择性。

关键词: Cu/Mg-MOF-74, CO₂, 吸附, 选择性, 孔结构, 光催化

Abstract:

Cu/Mg-MOF-74 has several advantages, such as high specific surface area, adjustable microporous structure, alkali metal active site, excellent CO₂ adsorption, and good photocatalytic activity. However, how the molar ratio of Cu/Mg (Cu/Mg ratio) affects its CO₂ adsorption selectivity in a simulated flue gas is still unclear. Here, a synthesized Cu/Mg-MOF-74, with series of Cu/Mg ratios, using the solvothermal method was analyzed about its CO₂ photocatalytic performance, CO₂ and N₂ uptake, and pore structure. The CO₂ adsorption selectivity was calculated to reveal the effect of Cu/Mg ratio on CO₂ and N₂ uptake and selectivity. The results indicate that the photocatalytic activity of Cu/Mg-MOF-74 for CO₂ reduction to CO and H₂ initially increases and then decreases with Cu/Mg ratio decreasing. At the Cu/Mg ratio of 0.6/0.4, the yield of CO and H₂ by photocatalytic reduction is the highest, showing up to 10.65 and 5.41 μmol·h⁻¹·g_cat⁻¹ (1 MPa, 150 ℃), respectively. Furthermore, CO₂ and N₂ uptakes of Cu/Mg-MOF-74 increase as the Cu/Mg ratio decreases, and the increase in CO₂ uptake is more pronounced. At the Cu/Mg ratio of 0.1/0.9, the CO₂ and N₂ uptakes are the largest, reaching 9.21 and 1.49 mmol·g⁻¹ (273.15 K, 100 kPa), respectively. Their area and volume of micropore (d₁ ≥ 0.7 nm) and ultramicropore (d₂ < 0.7 nm) increase as the Cu/Mg ratio decreases. At the Cu/Mg ratio of 0.22/0.78, the area and volume of micropores and ultramicropores are larger than those of Mg-MOF-74. The selectivity of Cu/Mg-MOF-74 increases correspondingly with Cu/Mg ratio decreasing and CO₂ concentration increasing. CO₂ adsorption on Cu/Mg-MOF-74 is a combination process of pore-filling and Mg²⁺chemical adsorption in which the micropore volume is the key factor affecting its adsorption performance. All above data demonstrate that modulating the Cu/Mg ratio can promisingly regulate the pore structure of Cu/Mg-MOF-74, CO₂ uptake, and selectivity.

Key words: Cu/Mg-MOF-74, CO₂, adsorption, selectivity, pore structure, photocatalysis

中图分类号:

TQ424

凌洁, 周安宁, 王文珍, 贾忻宇, 马梦丹. Cu/Mg比对Cu/Mg-MOF-74的CO₂吸附性能的影响[J]. 无机材料学报, 2023, 38(12): 1379-1386.

LING Jie, ZHOU Anning, WANG Wenzhen, JIA Xinyu, MA Mengdan. Effect of Cu/Mg Ratio on CO₂ Adsorption Performance of Cu/Mg-MOF-74[J]. Journal of Inorganic Materials, 2023, 38(12): 1379-1386.

图/表 11

图1 光催化反应釜照片及示意图

Fig. 1 Schematic and photo of photocatalytic reactor

表1 Cu/Mg-MOF-74的光催化性能

Table 1 Photocatalytic properties of Cu/Mg-MOF-74

Product	Yield/(μmol·h⁻¹·g_cat⁻¹)
Product	1/0	0.83/0.17	0.8/0.2	0.6/0.4	0.22/0.78	0.1/0.9	0/1
CO	3.60	6.6	10.07	10.65	8.45	5.65	-
H₂	1.68	1.895	2.04	5.41	5.07	4.36	-

图2 100 kPa条件下, Cu/Mg-MOF-74的CO2、N2吸附等温线

Fig. 2 Adsorption isotherms of CO2 and N2 of Cu/Mg-MOF-74 at 100 kPa (a) CO2 at 273.15 K; (b) CO2 at 288.15 K; (c) CO2 at 303.15 K; (d) N2 at 273.15 K; (e) N2 at 288.15 K; (f) N2 at 303.15 K

表2 不同Cu/Mg比Cu/Mg-MOF-74的孔结构

Table 2 Pore structure of Cu/Mg-MOF-74 according to different Cu/Mg ratios

Parameter		1/0	0.83/0.17	0.8/0.2	0.6/0.4	0.22/0.78	0.1/0.9	0/1
N₂adsorption	V_Total/(cm³·g^-1)^a	0.336	0.332	0.360	0.428	0.492	0.556	0.456
	V_Mic/(cm³·g^-1)^a	0.265	0.257	0.304	0.362	0.438	0.520	0.435
	S_Total/(m²·g^-1)^a	1035	1013	1235	1562	1917	2395	1611
	S_Mic/(m²·g^-1)^a	1020	996	1223	1533	1889	2371	1590
	d₁/ nm^b	0.774	0.769	0.760	0.767	0.763	0.763	0.751
CO₂adsorption	UV_Mic/(cm³·g^-1)^c	0.143	0.027	0.0735	0.181	0.246	0.322	0.129
	US_Mic/(m²·g^-1)^c	796.2	151.9	422.0	1003	1376	1800	714.7
	d₂/nm^b	0.612	0.699	0.681	0.612	0.555	0.539	0.578

图3 Cu/Mg比对模拟烟气中Cu/Mg-MOF-74的吸附选择性(S)的影响(303.15 K)

Fig. 3 Effect of Cu/Mg ratio on adsorption selectivity of Cu/Mg-MOF-74 in simulated flue gas at 303.15 K

图4 Cu/Mg-MOF-74的孔结构与CO2、N2吸附量关系

Fig. 4 Relationship between pore structure and CO2, N2 uptake of Cu/Mg-MOF-74 (a) VTotal and CO2; (b) VMic and CO2; (c) STotal and CO2; (d) SMic and CO2; (e) VTotal and N2; (f) VMic and N2; (g) STotal and N2; (h) SMic and N2

图5 Cu/Mg-MOF-74对模拟烟气中CO2的吸附过程

Fig. 5 Adsorption process of CO2 on Cu/Mg-MOF-74 in simulated flue gas

图S1 Cu/Mg-MOF-74的CO2-TPD

Fig. S1 CO2-TPD of Cu/Mg-MOF-74

图S2 Langmuir-Freundlich拟合模型(303.15 K)

Fig. S2 Langmuir-Freundlich fitting model of Cu/Mg-MOF-74 at 303.15 K

图S3 Cu/Mg-MOF-74的CO2吸附等温线(273.15 K)和孔径分布

Fig. S3 (a) CO2 adsorption isotherm at 273.15 K and (b) pore size distribution of Cu/Mg-MOF-74

表S1 CO2和N2在Cu/Mg-MOF-74上吸附的Langmuir-Freundlich模型拟合参数(303.15 K)

Table S1 Langmuir-Freundlich parameters of CO2 and N2 uptake on Cu/Mg-MOF-74 at 303.15 K and different Cu/Mg ratios

Parameter		1/0	0.83/0.17	0.8/0.2	0.6/0.4	0.22/0.78	0.1/0.9	0/1
CO₂	Q_sat/(mmol·g⁻¹)	11.11	19.03	23.33	44.74	7.44	10.65	9.49
	b	1.75×10⁻³	2.50×10⁻³	7.31×10⁻³	1.55×10⁻²	1.62×10⁻¹	1.83×10⁻¹	1.99×10⁻¹
	c	0.959	0.837	0.621	0.391	0.498	0.486	0.522
	R²	0.9999	0.9999	0.9991	0.9978	0.9952	0.9936	0.9939
N₂	Q_sat/(mmol·g⁻¹)	0.47	0.36	0.57	1.06	1.83	2.65	0.90
	b	2.17×10⁻³	3.09×10⁻³	2.70×10⁻³	2.90×10⁻³	2.08×10⁻³	2.24×10⁻³	3.25×10⁻³
	c	1.16	1.24	1.52	1.08	1.075	1.06	1.17
	R²	0.9999	0.9997	0.9998	0.9999	0.9999	0.9999	0.9998

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Cu/Mg比对Cu/Mg-MOF-74的CO₂吸附性能的影响

Effect of Cu/Mg Ratio on CO₂ Adsorption Performance of Cu/Mg-MOF-74

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