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

doi:10.15541/jim20230224

Abstract

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

CLC Number:

TQ424

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.

Figures/Tables 11

References 33

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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	-

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	-

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

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

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

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

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