Biomimetic active sites on monolayered metal–organic frameworks for artificial photosynthesis

Lan, Guangxu; Fan, Yingjie; Shi, Wenjie; You, Eric; Veroneau, Samuel S.; Lin, Wenbin

doi:10.1038/s41929-022-00865-5

Cited by 78 publications

(69 citation statements)

References 59 publications

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“…One such example on the rational design of MOF-based artificial enzymes was reported very recently by Lin and coworkers. 425 The study was based on the integration of active sites for the CO 2 RR and OER as well as proximal amino acids and other cofactors into tunable MOF monolayers. The MOF layers were first separately optimized for the CO 2 RR and OER by a diversification, selection and optimization strategy, and then coupled into a complete artificial photosynthesis scheme by the addition of a Co(bpy) 3 2+ redox mediator.…”

Section: Discussionmentioning

confidence: 99%

Molecular Catalysis of Energy Relevance in Metal–Organic Frameworks: From Higher Coordination Sphere to System Effects

et al. 2023

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The modularity and synthetic flexibility of metal–organic frameworks (MOFs) have provoked analogies with enzymes, and even the term MOFzymes has been coined. In this review, we focus on molecular catalysis of energy relevance in MOFs, more specifically water oxidation, oxygen and carbon dioxide reduction, as well as hydrogen evolution in context of the MOF–enzyme analogy. Similar to enzymes, catalyst encapsulation in MOFs leads to structural stabilization under turnover conditions, while catalyst motifs that are synthetically out of reach in a homogeneous solution phase may be attainable as secondary building units in MOFs. Exploring the unique synthetic possibilities in MOFs, specific groups in the second and third coordination sphere around the catalytic active site have been incorporated to facilitate catalysis. A key difference between enzymes and MOFs is the fact that active site concentrations in the latter are often considerably higher, leading to charge and mass transport limitations in MOFs that are more severe than those in enzymes. High catalyst concentrations also put a limit on the distance between catalysts, and thus the available space for higher coordination sphere engineering. As transport is important for MOF-borne catalysis, a system perspective is chosen to highlight concepts that address the issue. A detailed section on transport and light-driven reactivity sets the stage for a concise review of the currently available literature on utilizing principles from Nature and system design for the preparation of catalytic MOF-based materials.

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Section: Discussionmentioning

confidence: 99%

Molecular Catalysis of Energy Relevance in Metal–Organic Frameworks: From Higher Coordination Sphere to System Effects

et al. 2023

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“…[35][36][37] The chromophore ligands for light-responsive MOFs are usually selected from the class of porphyrin-, [15,[38][39][40][41] aryl- [28,[42][43][44][45][46][47][48][49][50][51] or transition metal-based motifs. [17,[52][53][54][55][56] In general, the MOF bandgap shifts were found to correlate well with the changes in the ionization potentials and electron affinities of isolated ligands with different substituents. [57] While ligand modifications provide excellent tunability of MOF bandgaps, the synthesis of ligands with varying conjugation lengths or functional groups is often challenging.…”

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confidence: 83%

Facile Energy Gap Tuning in Nanographene-MOFs

Zheng

Reji

Drummer

et al. 2023

Preprint

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The utilization of metal-organic frameworks (MOFs) in photocatalysis applications requires light-responsive architectures with tunable optical bandgaps. Here, we demonstrate a facile approach to optical bandgap tuning via post-synthetic modifica-tions of pbz-MOF-1, a Zr-based MOF with polyphenylene ligands. A simple reaction of pbz-MOF-1 with FeCl3 was shown to induce three different chemical reactions of the ligands: oxidative dehydrogenation, chlorination and one/two electron oxi-dation of the ligands. The result of these reactions was a gradual decrease in the optical bandgap from 2.95 eV to as little as 0.69 eV. Time-resolved optical spectroscopy and electron paramagnetic resonance spectroscopy, coupled with density functional theory calculations provide insights into the mechanisms of bandgap tuning using chemical oxidation methods. The facile bandgap tuning report here has promising application in the utilization of photo-responsive MOFs in photocatalysis, sensing and other light-triggered applications.

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“…4. Photocatalysis (Artificial Photosynthesis): By mimicking photosynthesis, MOZs, or MOFs combined with certain amino acids, have successfully converted water and CO 2 to oxygen and fuel sources through photocatalysis (27). In other words, MOZs supplement the oxygen supply system as well as support longdistance missions with methane production.…”

Section: Microporous Materials and In-situ Resource Utilizationmentioning

confidence: 99%

“…With the expected growth in space exploration, there is likely to be unintended consequences such as the rapid proliferation of satellite and satellite debris. The increasing demand for space goods and services indicates a proliferation of satellite constellations and other LEO objects; an estimated 100,000 satellites majorly proposed by broadband satellite companies, 26 observational satellite companies, 27 CubeSats/small satellite companies, 28 and others, are projected to be in orbit by 2030 (81). While there are an estimated 4,500 active satellites, NASA estimates 9,000 metric tons of space debris composed of inactive satellites, partial rocket and satellite components, and micrometeroids are unaccounted for, with 70% of debris in LEO (82).…”

Section: Satellite Servicing/debrismentioning

confidence: 99%

Space Exploration: The Role for Public-Private Research and Development Partnerships

2023

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Biomimetic active sites on monolayered metal–organic frameworks for artificial photosynthesis

Cited by 78 publications

References 59 publications

Molecular Catalysis of Energy Relevance in Metal–Organic Frameworks: From Higher Coordination Sphere to System Effects

Molecular Catalysis of Energy Relevance in Metal–Organic Frameworks: From Higher Coordination Sphere to System Effects

Facile Energy Gap Tuning in Nanographene-MOFs

Space Exploration: The Role for Public-Private Research and Development Partnerships

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