Organic-site-dominated cooperative catalysis in defect-tolerant 2D lanthanide MOFs for direct CO2 valorization and DFT calculations

doi:10.1016/S1872-2067(26)65094-2

Abstract

Abstract:

The catalytic valorization of CO₂ into value-added chemicals remains a grand challenge in sustainable catalysis. Here we report a defect-tolerant two-dimensional thulium-organic framework, {[Tm(NH₂-HPPDC)(DMF)₂]·2DMF·2H₂O}_n (NUC-151), constructed through a dimensionality-reduction and ligand-functionalization strategy. Upon activation, NUC-151a develops well-ordered in-plane nanopores (14.9 × 10.7 Å²) densely populated with Lewis-acidic Tm³⁺ centers, Lewis-basic amino/pyridyl moieties, and hydrogen-bond-donating carboxyl groups. The synergistic interplay among these multifunctional sites establishes an acid-base-hydrogen-bond cooperative environment that efficiently catalyzes CO₂-epoxide cycloaddition under mild, co-catalyst-assisted conditions, affording nearly quantitative yields even under simulated dry and humid flue-gas atmospheres. Density functional theory analyses identify CO₂ insertion as the universal rate-determining step, with activation barriers following the trend -NH₂ < TmO₆ < -COOH, thereby elucidating a hierarchy of Lewis-acid activation, base-assisted charge stabilization, and hydrogen-bond facilitation. The defect-tolerant 2D architecture sustains high activity and recyclability by preserving accessible organic active sites even upon partial hydration of metal centers. This study unveils an organic-site-dominated cooperative mechanism for CO₂ fixation and provides a general design principle for moisture-resilient, multifunctional MOFs operating directly under flue-gas conditions.

Key words: Acid-base-hydrogen-bond synergy, Organic-site-dominated catalysis, Defect-tolerant metal-organic frameworks, Flue-gas CO₂ fixation, Density functional theory mechanism

Yang Fei, Qingjuan Lei, Liming Fan, Tuoping Hu, Qi-Pin Qin, Xiutang Zhang. Organic-site-dominated cooperative catalysis in defect-tolerant 2D lanthanide MOFs for direct CO₂ valorization and DFT calculations[J]. Chinese Journal of Catalysis, 2026, 89: 353-366.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65094-2

https://www.cjcatal.com/EN/Y2026/V89/I10/353

Figures/Tables 12

Scheme 1. Conceptual illustration of the organic-site-dominated design strategy for NUC-151, highlighting the stepwise functional evolution of the ligand framework while preserving the organic backbone. The reorganization of amino and carboxyl groups gives rise to an organic-site-driven catalytic microenvironment.

Scheme 2. Synthetic procedure of NH2-H4PPDC.

Fig. 1. (a-c) SEM images of NUC-151. (d) XPS survey spectra of NUC-151. XPS spectra of C (e), N (f), O (g), and Tm (h) in NUC-151.

Fig. 2. The coordination mode of NH2-HPPDC3- ligand (a), two-dimensional sheet of NUC-151, (green polyhedra = TmO8 units, the nanochannels were highlighted with pink spheres, H atoms are omitted for clarity) (b?d) and topology of NUC-151 (e).

Table 1 Cycloaddition reaction of CO2 with 2-(chloromethyl) epoxyethane (CE) under various conditions a.

Entry	NUC-151a (mol%)	n-Bu₄NBr (mol%)	P (MPa)	T (°C)	Time (h)	Yield ^b (%)
1	0.05	1.0	0.1	35	24	18
2	—	1.0	0.1	35	24	12
3	0.06	1.0	0.1	35	24	37
4	0.07	1.0	0.1	35	24	49
5	0.08	1.0	0.1	35	24	55
6	0.09	1.0	0.1	35	24	59
7	0.10	1.0	0.1	35	24	61
8	0.10	1.0	0.1	45	24	82
9	0.10	1.0	0.1	55	24	99
10	0.10	1.0	0.1	65	20	99
11	0.10	1.0	0.1	75	16	99
12	0.10	1.0	0.1	85	12	99
13	0.10	1.0	0.4	85	10	99
14	0.10	1.0	0.6	85	8	99
15	0.10	1.0	0.8	85	6	99
16	0.10	1.0	1.0	85	4	99

Fig. 3. The reaction pathway and energy profiles for PO and CO2 to PC over TmO6 catalytic site.

Fig. 4. The reaction pathway and energy profiles for PO and CO2 to PC over -COOH catalytic site.

Table 2 Energy barriers (kcal/mol) in distinct steps during the cycloaddition process over different units.

Catalytic unit	ring-opening	CO₂ insertion	ring-closing
TmO₆	6.7	13.6	4.7
COOH	4.7	19.8	10.7
NH₂	5.4	12.3	5.3

Fig. 5. The reaction pathway and energy profiles for PO and CO2 to PC over -NH2 catalytic site.

Fig. 6. Comparison of the reaction pathways and energy profiles for the conversion of PO and CO2 to PC over three active sites.

Table 3 The cycloaddition reactions of CO2 with various epoxides with NUC-151a as catalyst.a

Entry	Yield ^b (%)	TON ^c	TOF ^d
1	99	990	247
2	99	990	247
3	98	980	245
4	99	990	247
5	96	960	240
6	97	970	242
7	95	950	237
8	45	450	112
9	96	960	240

Fig. 7. The proposed reaction mechanism of the cycloaddition of CO2 with epoxides.

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Organic-site-dominated cooperative catalysis in defect-tolerant 2D lanthanide MOFs for direct CO₂ valorization and DFT calculations

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Entry	Yield ^b (%)	TON ^c	TOF ^d
1	99	990	247
2	99	990	247
3	98	980	245
4	99	990	247
5	96	960	240
6	97	970	242
7	95	950	237
8	45	450	112
9	96	960	240

Entry	Yield ^b (%)	TON ^c	TOF ^d
1	99	990	247
2	99	990	247
3	98	980	245
4	99	990	247
5	96	960	240
6	97	970	242
7	95	950	237
8	45	450	112
9	96	960	240

Entry	Yield ^b (%)	TON ^c	TOF ^d
1	99	990	247
2	99	990	247
3	98	980	245
4	99	990	247
5	96	960	240
6	97	970	242
7	95	950	237
8	45	450	112
9	96	960	240

Entry	Yield ^b (%)	TON ^c	TOF ^d
1	99	990	247
2	99	990	247
3	98	980	245
4	99	990	247
5	96	960	240
6	97	970	242
7	95	950	237
8	45	450	112
9	96	960	240

Entry	Yield ^b (%)	TON ^c	TOF ^d
1	99	990	247
2	99	990	247
3	98	980	245
4	99	990	247
5	96	960	240
6	97	970	242
7	95	950	237
8	45	450	112
9	96	960	240

Entry	Yield ^b (%)	TON ^c	TOF ^d
1	99	990	247
2	99	990	247
3	98	980	245
4	99	990	247
5	96	960	240
6	97	970	242
7	95	950	237
8	45	450	112
9	96	960	240