缺陷耐受的二维镧系金属有机框架中有机位点主导催化的CO2增值及密度泛函计算

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

摘要/Abstract

摘要：

二氧化碳(CO₂)的高效转化是实现碳资源化利用和缓解温室气体排放的重要途径之一. 其中, CO₂与环氧化物的环加成反应可一步高效制备高附加值的环碳酸酯, 该反应具有100%的原子经济性、无副产物生成等显著优势, 是当前CO₂转化领域的研究热点. 然而, 现有催化体系多依赖金属中心作为主要活性位点, 在潮湿或复杂气氛中, 金属中心易发生水合失活, 导致催化活性大幅下降、循环稳定性不足, 严重限制了其在工业烟道气直接转化场景中的应用. 因此, 开发在模拟烟道气条件下仍保持高活性与稳定性的多位点协同催化材料具有重要意义.

本研究针对现有催化剂依赖金属中心的不足, 通过维度降低与配体功能化策略, 选用氨基功能化的四酸配体(NH₂-H₄PPDC)与金属铥, 采用溶剂热法成功构筑了一种缺陷耐受型二维铥基有机框架材料(NUC-151). 通过热活化处理得到的活化形式NUC-151a, 形成了规整的面内纳米孔道, 其孔径尺寸为14.9 × 10.7 Å², 该二维孔道结构能为反应物提供高效的传质通道. 孔道内密集排布着路易斯酸性的Tm³⁺中心、路易斯碱性的氨基/吡啶基团以及氢键给体羧基, 三者共同构建了一个高度集成、功能互补的“酸-碱-氢键”协同催化微环境. 在温和条件(80 ºC、1 MPa CO₂)及四丁基溴化铵(n-Bu₄NBr)助催化下, 该催化体系对环氧丙烷、环氧氯丙烷等多种环氧化物均表现出优良的催化活性与广泛的底物兼容性. 尤为重要的是即便在模拟干燥(15% CO₂/85% N₂)及潮湿烟道气氛中, 该催化体系仍能维持> 90%和> 84%的转化率, 展现出卓越的实际应用潜力. 为深入理解多位点催化机制, 采用密度泛函理论(DFT)系统研究了TmO₆, -NH₂和-COOH三种代表性位点的催化路径. 结果表明, CO₂插入步骤为三者共同的速率控制步骤, 其活化能垒顺序为-NH₂ (12.3 kcal mol^‒1) < TmO₆ (13.6 kcal mol^‒1) < -COOH (19.8 kcal mol^‒1), 定量揭示了氨基位点通过其双功能特性(路易斯碱性与氢键给体能力)在稳定过渡态、降低反应能垒方面的主导作用. 这种“有机位点主导”的协同机制, 使得材料在金属中心可能发生部分水合的情况下, 仍能通过保留完整活性的有机官能团维持高催化性能, 显示出面向烟道气转化的优势. 循环实验及多种表征表明, NUC-151a在连续使用多次后仍保持结构和催化性能稳定, 进一步验证了其工业应用潜力.

综上, 本工作不仅开发了一类在模拟烟道气条件下性能稳定的金属有机框架(MOF)催化剂, 更重要的是通过实验与理论的结合, 阐明了一种“有机位点主导、多官能团协同”的新型催化机制, 突破了传统MOF催化对金属中心的单一依赖. 该研究为设计面向真实工业烟气直接转化、兼具高活性、耐湿性与结构稳定性的下一代催化材料提供了清晰的机理解读和可行的设计范式.

关键词: 酸碱氢键协同作用, 有机位点主导的催化作用, 缺陷耐受型金属有机框架, 烟气二氧化碳固定, 密度泛函理论研究

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

费杨, 雷青娟, 范黎明, 胡拖平, 覃其品, 张修堂. 缺陷耐受的二维镧系金属有机框架中有机位点主导催化的CO₂增值及密度泛函计算[J]. 催化学报, 2026, 89: 353-366.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65094-2

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

图/表 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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缺陷耐受的二维镧系金属有机框架中有机位点主导催化的CO₂增值及密度泛函计算

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

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Metrics

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