Thiadiazole-based Rare Earth Metal-organic Frameworks for Efficient Catalysis of CO2 Cycloaddition Reactions

doi:10.7503/cjcu20250196

Abstract

Abstract:

A series of novel isostructural three-dimensional rare earth metal-organic frameworks（MOFs），［RE₄（BTDI）₃（DMF）₄］·solv（RE-BTDI， RE=Er， Dy， Y）， was synthesized by solvothermal method using tetracarboxylic acid ligand containing thiadiazole groups， 5，5′-（benzothiadiazole-4，7-diyl）diisophthalic acid（H₄BTDI）， and rare earth metal nitrates. The rare earth metal nodes on the frameworks of RE-BTDI are Lewis acidic sites which was confirmed qualitatively and quantitatively by Py-IR and NH₃-TPD. Meanwhile， the thiadiazole groups introduced by ligands can be used as polar sites to enhance the CO₂ adsorption performance of these materials. Under the synergy of the Lewis acidic sites and thiadiazole groups， RE-BTDI showed good catalytic activity for the cycloaddition reaction of CO₂ and a series of epoxides. Under the conditions of 80 ℃， 1 MPa CO₂， 0.1%（molar fraction） RE-BTDI catalyzed the cycloaddition reaction of CO₂ and styrene oxide for 5 h， the yield of styrene cyclic carbonate can reach 90%， and after 5 rounds of cyclic catalysis， the catalytic activity and catalyst structure maintained well. In addition， for other epoxides， the yields of the corresponding cyclic carbonate products can reach 92.5% to 99.0% catalyzed by RE-BTDI under relatively mild conditions.

Key words: Metal organic framework, Rare earth, Thiadiazole, Heterogeneous catalysis, CO₂ cycloaddition

CLC Number:

O643

TrendMD:

GUO Jingpeng, ZHANG Hangchuan, WEI Na, WANG Shu, JIANG Hongbo, ZHAO Zhen. Thiadiazole-based Rare Earth Metal-organic Frameworks for Efficient Catalysis of CO₂ Cycloaddition Reactions[J]. Chem. J. Chinese Universities, 2025, 46(10): 20250196.

Figures/Tables 11

Table 1 Crystal data for Er-BTDI

Compound	Er⁃BTDI	D_c/（Mg∙m^‒3）	2.076
Empirical formula	C₇₈H₅₂N₁₀O₂₈S₃Er₄	μ/mm^‒1	4.614
Formula weight	2342.51	F（000）	1134.0
Wavelength/nm	0.071073	Range for data collection/（°）	2.725—27.083
Crystal system	Triclinic	Reflections collected	6600
Space group	P $1 ¯$	Max. and min. transmission	0.746， 0.527
a/nm	1.08882（3）	T/K	293（2）
b/nm	1.20504（3）	Data/restraints/parameters	6600/18/97
c/nm	1.58149（4）	Final R indices ［I > 2σ（I）］ ^*	R₁=0.0204， wR₂=0.0470
V/nm³	1.87327	R indices（all data）	R₁=0.0369， wR₂=0.0495
Z	1

Table 1 Crystal data for Er-BTDI

Compound	Er⁃BTDI	D_c/（Mg∙m^‒3）	2.076
Empirical formula	C₇₈H₅₂N₁₀O₂₈S₃Er₄	μ/mm^‒1	4.614
Formula weight	2342.51	F（000）	1134.0
Wavelength/nm	0.071073	Range for data collection/（°）	2.725—27.083
Crystal system	Triclinic	Reflections collected	6600
Space group	P $1 ¯$	Max. and min. transmission	0.746， 0.527
a/nm	1.08882（3）	T/K	293（2）
b/nm	1.20504（3）	Data/restraints/parameters	6600/18/97
c/nm	1.58149（4）	Final R indices ［I > 2σ（I）］ ^*	R₁=0.0204， wR₂=0.0470
V/nm³	1.87327	R indices（all data）	R₁=0.0369， wR₂=0.0495
Z	1

Table 2 Cycloaddition reaction of SO（20 mmol） with CO2 under different reaction conditions catalyzed by Er-BTDI

Entry	Molar fraction of catalyst（%）	Molar fraction of co⁃catalyst（%）	Pressure ofCO₂/MPa	Temperature/℃	Time/h	Conversion ^a （%）	Selectivity（%）	TON ^b
1	0.10	5.00	1.00	25	4	1.0	99.9	10
2	0.10	5.00	1.00	40	4	4.3	99.9	43
3	0.10	5.00	1.00	60	4	60.5	99.9	604
4	0.10	5.00	1.00	80	4	81.1	99.9	810
5	0.10	5.00	1.00	100	4	96.8	99.9	967
6	0.10	5.00	0.50	80	4	53.7	99.9	536
7	0.10	5.00	0.75	80	4	74.9	99.9	748
8	0.10	5.00	1.25	80	4	82.1	99.9	820
9	0.10	5.00	1.50	80	4	83.1	99.9	830
10	0.10	5.00	1.00	80	2	55.4	99.9	553
11	0.10	5.00	1.00	80	3	72.9	99.9	728
12	0.10	5.00	1.00	80	5	90.0	99.9	899
13	0.10	5.00	1.00	80	6	91.5	99.9	914
14	0.10	2.50	1.00	80	4	59.8	99.9	597
15	0.10	3.75	1.00	80	4	79.8	99.9	797
16	0.10	6.25	1.00	80	4	85.0	99.9	849
17	0.10	7.00	1.00	80	4	81.2	99.9	811
18	0.05	5.00	1.00	80	4	73.4	99.9	1467
19	0.15	5.00	1.00	80	4	86.3	99.9	575

Table 3 Comparison of catalytic activity for Er-BTDI and other MOFs catalysts

Catalyst	Pressure/MPa	Temperature/℃	Time/h	Conversion^*（%）	Reference
Tb⁃MOF	1.0	100	10	84.5	［27］
ZIF⁃67（TBAB）	2.5	120	5	43.0	［28］
SiO₂@MOF	2.0	80	24	71.0	［29］
HE⁃MOF⁃74	1.0	100	8	86.8	［30］
Er⁃BTDI	1.0	80	5	90.0	This work

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Thiadiazole-based Rare Earth Metal-organic Frameworks for Efficient Catalysis of CO₂ Cycloaddition Reactions

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