Cooperative Interplay of Brønsted Acid and Lewis Acid Sites in MIL-101(Cr) for Cross-Dehydrogenative Coupling of C–H Bonds

Chen, Jingwen; Zhang, Yuanyuan; Chen, Xiaoling; Dai, Siyun; Bao, Zongbi; Yang, Qiwei; Ren, Qilong; Zhang, Zhiguo

doi:10.1021/acsami.0c20369

Cited by 16 publications

(10 citation statements)

References 69 publications

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“…Recently, Chen et al [ 163 ] reported the catalytic property of MIL-101(Cr)-SO 3 H for the aerobic cross-dehydrogenation coupling (CDC) reaction ( Scheme 8 ). MIL-101(Cr)-SO 3 H exhibited quite good catalytic activity in CDC reaction with a product yield of 63% and high selectivity of 98%, which was much higher than that of typical commercial solid acid catalysts.…”

Section: Applicationsmentioning

confidence: 99%

Advances in Metal-Organic Frameworks MIL-101(Cr)

Zou

Dong

Zhao

2022

IJMS

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MIL-101(Cr) is one of the most well-studied chromium-based metal–organic frameworks, which consists of metal chromium ion and terephthalic acid ligand. It has an ultra-high specific surface area, large pore size, good thermal/chemical/water stability, and contains unsaturated Lewis acid sites in its structure. Due to the physicochemical properties and structural characteristics, MIL-101(Cr) has a wide range of applications in aqueous phase adsorption, gas storage and separation, and catalysis. In this review, the latest synthesis of MIL-101(Cr) and its research progress in adsorption and catalysis are reviewed.

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Section: Applicationsmentioning

confidence: 99%

Advances in Metal-Organic Frameworks MIL-101(Cr)

Zou

Dong

Zhao

2022

IJMS

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“…22 A conjugated framing effect promoted the thermally irreversible activation from O 2 to ROS via an EnT event under another photon excitation. The confined effect of the MOF ensured that the in situ formed singlet oxygen ( 1 O 2 ) combined with carbon radicals to generate peroxy radicals, 23 which further interact with the unsaturated coordinated cerium ions to facilitate their hydrolysis to selectively obtain products containing the carbonyl group 24 and recover the mixed-valence oxygen bridge for the next catalytic cycle. 19 As far as we are aware, this represents the first case of a binuclear Ce−MOF as an artificial monooxygenase, which enables a synergistic two parallel photons strategy for the extremely high activity and selectivity for inert C(sp 3 )−H bonds oxidation under mild conditions utilizing environmentally friendly oxygen instead of expensive or toxic oxidants, providing an environmentally benign route for the direct activation and oxidation of inert alkanes.…”

Section: ■ Introductionmentioning

confidence: 95%

A Binuclear Cerium-Based Metal–Organic Framework as an Artificial Monooxygenase for the Saturated Hydrocarbon Aerobic Oxidation with High Efficiency and High Selectivity

Zhao

Wang

et al. 2022

ACS Catal.

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Artificial enzymatic systems have emerged in the field of biomimetic catalysis by constructing specific catalytic centers of enzymes. Inspired by the high activity of natural monooxygenase for the oxidation transformation, several binuclear Cu/Fe-based metal−organic frameworks (MOFs) have been frequently used as oxidation catalysts, yet rarely reports of MOFs with other metals nodes have been reported to date. In this work, by the ingenious decoration of binuclear Ce−O−Ce moieties and anthraquinone groups with good oxygen activation ability in one framework, an MOF-supported artificial binuclear cerium monooxygenase was obtained for the highly selective oxidation of inert C(sp 3 )−H bonds. The single-crystal structural study reveals that the molecule-level modularity with a binuclear Ce−O−Ce moiety design in the MOF creates a confined microenvironment to offer the ordered distribution of highly dense substrate-accessible active sites throughout the architecture. After photoexcitation, the Ce−O−Ce moieties trigger a ligand-to-metal charge-transfer (LMCT) event to form an oxygen bridge radical, which abstracts a hydrogen atom from the C(sp 3 )−H bond to generate a carbon-centered radical through a typical hydrogen atom transfer (HAT) process. These carbon-centered radicals rapidly combine the reactive oxygen species (ROS) produced by the anthraquinone groups via an energy transfer (EnT) process to generate the alkyl peroxy radical intermediates, which are easily trapped by another unsaturated coordinated cerium ions to further facilitate their hydrolysis for the selective formation of carbonyl products. This anthraquinone-functionalized metal−organic framework containing binuclear cerium catalytic centers resembling the active sites of natural monooxygenase exhibits the unique catalytic selectivity (>97%) and high activity, which represent the first example of the MOF constructed from metals different from that of natural monooxygenase for applying to the oxidation of alkanes, expanding the selection range of metal centers in the artificial monooxygenase. Taking advantage of the heterogeneity of the MOF, the Ce−MOF was recycled five times without a decrease in its selectivity and activity and possessed broader applicability for the substrate with inert C−H bonds, providing a blueprint for designing new artificial monooxygenase for the inert alkane oxidation.

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“…6). 57 Compared to the pristine MIL-101(Cr), MIL-101(Cr)-SO 3 H exhibited a superior yield and selectivity towards C(sp 3 )-H alkylation due to the synergistic effect between the Lewis acid (Cr clusters) and Brønsted acid (-SO 3 H groups on the linker) sites in its framework. The product yields slightly decreased when large-size starting materials were used.…”

Section: Integrated Anmentioning

confidence: 99%