Metal–Organic Framework with Dual Active Sites in Engineered Mesopores for Bioinspired Synergistic Catalysis

Quan, Yangjian; Song, Yang; Shi, Wenjie; Xu, Ziwan; Chen, Justin S.; Jiang, Xiaomin; Wang, Cheng; Lin, Wenbin

doi:10.1021/jacs.0c02966

Cited by 66 publications

(55 citation statements)

References 65 publications

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“…As a promising class of crystalline porous materials with well-defined architecture and high specific surface area, metal–organic frameworks (MOFs) are standing on the forefront of chemistry and material science. − In virtue of their structural and functional diversity, MOFs have been demonstrated as prominent platforms in a large variety of environmental and energy-related applications, such as heterogeneous catalysis. − The modular nature of MOFs allows metal sites to be precisely tuned for optimizing their catalytic performance. − Significant progress has been made in this regard, while superior catalytic performance is still being pursued among MOFs.…”

Section: Introductionmentioning

confidence: 99%

A Practice of Reticular Chemistry: Construction of a Robust Mesoporous Palladium Metal–Organic Framework via Metal Metathesis

Kong

Zhou

et al. 2021

J. Am. Chem. Soc.

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Constructing stable palladium(II)-based metal−organic frameworks (MOFs) would unlock more opportunities for MOF chemistry, particularly toward applications in catalysis. However, their availability is limited by synthetic challenges due to the inertness of the Pd−ligand coordination bond, as well as the strong tendency of the Pd(II) source to be reduced under typical solvothermal conditions. Under the guidance of reticular chemistry, herein, we present the first example of an azolate Pd-MOF, BUT-33(Pd), obtained via a deuterated solvent-assisted metal metathesis. BUT-33(Pd) retains the underlying sodalite network and mesoporosity of the template BUT-33(Ni) and shows excellent chemical stability (resistance to an 8 M NaOH aqueous solution). With rich Pd(II) sites in the atomically precise distribution, it also demonstrates good performances as a heterogeneous Pd(II) catalyst in a wide application scope, including Suzuki/Heck coupling reactions and photocatalytic CO 2 reduction to CH 4 . This work highlights a feasible approach to reticularly construct noble metal based MOFs via metal metathesis, in which various merits, including high chemical stability, large pores, and tunable functions, have been integrated for addressing challenging tasks.

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Section: Introductionmentioning

confidence: 99%

A Practice of Reticular Chemistry: Construction of a Robust Mesoporous Palladium Metal–Organic Framework via Metal Metathesis

Kong

Zhou

et al. 2021

J. Am. Chem. Soc.

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“…Metal–organic frameworks (MOFs), as highly porous and crystalline polymers, have attracted considerable attention in recent years for applications spanning gas adsorption/separation, sensing, biomedicine and catalysis [1–7] . These materials have been specifically attractive on account of containing designable structures and tunable physicochemical properties.…”

Section: Methodsmentioning

confidence: 99%

Nature‐Inspired Construction of MOF@COF Nanozyme with Active Sites in Tailored Microenvironment and Pseudopodia‐Like Surface for Enhanced Bacterial Inhibition

et al. 2020

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Metal–organic frameworks (MOFs) have sparked increasing interest in mimicking the structure and function of natural enzymes. However, their catalytic and therapeutic efficiency are unsatisfactory due to the relatively lower catalytic activity. Herein, inspired by nature, a MOF@COF nanozyme has been designed as a high‐efficiency peroxidase mimic, with the metallic nodes of MOFs as active centres, the hierarchical nanocavities produced by the growth of covalent organic frameworks (COFs) as binding pockets to form tailored pore microenvironment around active sites for enriching and activating substrate molecules, to perform enhanced bacterial inhibition. Furthermore, the pseudopodia‐like surface of the COFs “skin” enabled the system to catch the bacteria effectively for further amplifying the therapeutic efficiency of MOF‐based nanozyme. We believe that the present study will not only facilitate the design of novel nanozymes, but also broaden the biological usage of MOF/COF‐based hybrid materials.

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“…In fact, the microenvironment effect on the performance of heterogeneous catalysts and the underlying structure–performance relationship are fundamental issues at research frontiers in materials science and heterogeneous catalysis and remain largely elusive. On account of the infinite structural and component diversity of MOFs, it is expected that attractive biomimetic features would be brought about by microenvironment modulation in MOF-based catalytic system. ,, Moreover, the atomically precise microenvironment and clear location of catalytic sites are able to provide clear pictures/evidence to unveil the structure–performance relationship in microenvironment-induced catalysis. Therefore, it is of significance to summarize this research field, though in its nascent stage, and provide deep insight into the critical roles of the microenvironment in MOF-based catalysis, thereby promoting its further development.…”

Section: Introductionmentioning

confidence: 99%

Microenvironment Modulation in Metal–Organic Framework-Based Catalysis

2021

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Metrics & MoreArticle Recommendations CONSPECTUS:The fine design and regulation of catalysts play critical roles in the development of catalysis. The microenvironment, which gives rise to unique spatial structures and electronic properties around catalytic sites, has been proven to dramatically regulate catalytic behavior in enzymes and homogeneous catalysis. However, understanding the microenvironment modulation (MEM) of catalytic sites remains challenging and very limited in heterogeneous catalysis mainly due to the lack of structural precision and/or tailorability of traditional solid catalysts. Among diverse materials, metal−organic frameworks (MOFs), a class of porous crystalline solids, have been intensively studied as heterogeneous catalysts in recent years. The atomically precise and well tunable structures of MOFs make them an ideal platform for rationally regulating the microenvironment surrounding catalytic sites. Accordingly, their well-defined structures hold great promise for elucidating how the microenvironment modulation affects the resulting catalytic performance. Nevertheless, the investigations of accurate control over the microenvironment of catalytic sites in MOFs for modulated catalysis are still very limited. Therefore, it is of great importance to summarize the related results and provide in-depth insights into microenvironment modulation in MOF-based catalysis, accelerating the future development of this emerging research topic.In this Account, we have presented a summary of our recent attempts to optimize the catalytic performance of MOF-based materials via microenvironment modulation. In view of the unique component and structural advantages of MOFs, we deliver the general fundamentals for rational control over the microenvironment in MOF-based catalysis. Initially, the great opportunities brought about by MOFs for accurate control over microenvironment engineering, including the origin of abundant active sites, flexible regulation strategies, and well-defined structure, are introduced in detail. In the next section, we focus on the specific strategies of microenvironment modulation in MOF-based catalysis, which dominate the molecular/electron-transfer process and regulate the intrinsic activity of catalytic sites. Meanwhile, the related chemical basis and underlying structure−property relationship behind the enhanced catalytic performance will be highlighted. Finally, the major challenges and future outlooks on the microenvironment modulation in MOF-based catalysis will be further discussed. It is expected that this Account would provide an understanding of the importance of microenvironment modulation around catalytic sites in MOF-based catalysts and afford significant inspiration toward enhanced performance by microenvironment engineering in heterogeneous catalysis.

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Metal–Organic Framework with Dual Active Sites in Engineered Mesopores for Bioinspired Synergistic Catalysis

Cited by 66 publications

References 65 publications

A Practice of Reticular Chemistry: Construction of a Robust Mesoporous Palladium Metal–Organic Framework via Metal Metathesis

A Practice of Reticular Chemistry: Construction of a Robust Mesoporous Palladium Metal–Organic Framework via Metal Metathesis

Nature‐Inspired Construction of MOF@COF Nanozyme with Active Sites in Tailored Microenvironment and Pseudopodia‐Like Surface for Enhanced Bacterial Inhibition

Microenvironment Modulation in Metal–Organic Framework-Based Catalysis

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