Vertex Strategy in Layered 2D MOFs: Simultaneous Improvement of Thermodynamics and Kinetics for Record C₂H₂/CO₂ Separation Performance

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(16), С. 9254 - 9263

Опубликована: Апрель 13, 2023

Developing adsorbents with multiple merits in capacity, selectivity, mass transfer, and stability toward C2H2/CO2 separation is crucial challenging for producing high-purity C2H2 advanced polymers the electronic industry. Here, we demonstrate a vertex strategy to create combining these through rationally designing groups of wavy-shaped framework layered 2D metal-organic frameworks (MOFs) finely regulate local conformation stacking interactions, which creates optimal inter- intralayer space realize simultaneous improvement adsorption thermodynamics kinetics. Two new hydrolytically stable MOFs, ZUL-330 ZUL-430, were prepared, diverse experiments modeling on both equilibrium diffusion performed. Record selectivities coupled extraordinary dynamic capacities achieved mixtures different proportions (50/50 or 10/5, v/v), along small barrier fast transfer. Consequently, polymer-grade (99.9%) electronic-grade (99.99%) obtained excellent productivities up ∼6 mmol cm-3.

Язык: Английский

---

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

Chemical Reviews, Год журнала: 2023, Номер 123(10), С. 6545 - 6611

Опубликована: Май 15, 2023

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

Язык: Английский

---

Pore Size Modulation in Flexible Metal‐Organic Framework Enabling High Performance Gas Sensing

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(26)

Опубликована: Апрель 28, 2023

Pore size plays a critical role in determining the performance of metal-organic frameworks (MOFs) catalysis, sensing, and gas storage or separation. However, revealing pore-size/property relationship remains extremely challenging because ideal structure models possessing different pore sizes but having same components are lacking. In this work, solvent-coordination directed swelling method was developed for modulating ratio between large narrow phases flexible MOF, MIL-88B. Pore-size-dependent sensitivity selectivity were studied first time MIL-88B samples. The optimized MIL-88B-20 % sample showed one best sensing performances among all reported MOF-based H2 S-sensing materials. This work not only provides to synthesize pore-size properties, also may inspire development high-performance

Язык: Английский

---

Steric Hindrance-Induced Dehydration Promotes Cation Selectivity in Trans-Subnanochannel Transport

ACS Nano, Год журнала: 2023, Номер 17(13), С. 12629 - 12640

Опубликована: Июнь 23, 2023

Dehydration is a basic phenomenon in ion transport through confined nanochannels, but how it affects trans-membrane selectivity has not been understood due to lack of characterization techniques and suitable pore structures. Herein, hydration number distributions typical alkali metal ions were characterized by combining uniform subnanochannels ZIF-8-based membranes with the situ liquid time-of-flight secondary mass spectrometry (ToF-SIMS) technique, revealing that steric hindrance induced dehydration neutral ZIF-8 windows. The reduction size partial increased intrapore velocity for monovalent cations. highest entropy value maximum changes resulting from drove fast efficient selective Li+ over other alkaline ions, leading Li+/Rb+ 5.2. at entrance membrane pores was shown account majority overall barriers, being dominant element transport. High energy (>1500 kJ/mol) hindered earth achieving ultrahigh monovalent/bivalent cation (∼104). These findings uncover crucial role barriers size-based trans-subnanochannel transport, providing guidelines designing specific sizes promote desired solutes.

Язык: Английский

---

Highly defective ultra-small tetravalent MOF nanocrystals

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Апрель 23, 2024

Abstract The size and defects in crystalline inorganic materials are of importance many applications, particularly catalysis, as it often results enhanced/emerging properties. So far, applying the strategy modulation chemistry has been unable to afford high-quality functional Metal–Organic Frameworks (MOFs) nanocrystals with minimized while exhibiting maximized defects. We report here a general sustainable for design highly defective ultra-small tetravalent MOFs (Zr, Hf) crystals (ca. 35% missing linker, 4–6 nm). Advanced characterizations have performed shed light on main factors governing crystallization mechanism identify nature nanoMOFs showed exceptional performance peptide hydrolysis reaction, including high reactivity, selectivity, diffusion, stability, show emerging tailorable reactivity selectivity towards bond formation simply by changing reaction solvent. Therefore, these M(IV)-MOFs particles open new perspectives development heterogeneous MOF catalysts dual functions.

Язык: Английский

---

Analysis of metal–organic framework-based photosynthetic CO2 reduction

Nature Synthesis, Год журнала: 2024, Номер 3(3), С. 307 - 318

Опубликована: Март 7, 2024

Язык: Английский

---

Metal-organic frameworks for biomedical applications: A review

Advances in Colloid and Interface Science, Год журнала: 2024, Номер 331, С. 103210 - 103210

Опубликована: Июнь 5, 2024

Язык: Английский

---

Diffusion-programmed catalysis in nanoporous material

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 3, 2025

Abstract In the realm of heterogeneous catalysis, diffusion reactants into catalytically active sites stands as a pivotal determinant influencing both turnover frequency and geometric selectivity in product formation. While accelerated can elevate reaction rates, it often entails compromise selectivity. Porous catalysts, including metal-organic covalent organic frameworks, confront formidable obstacles regulating reactant rates. Consequently, chemical functionality catalysts typically governs This study presents an approach harnessing length to achieve improved manipulation reactant-active site residence time at augment kinetics. Through deployment thin film composed porous framework catalyst, we illustrate how programming within cross-flow microfluidic catalytic reactor concurrently amplify (exceeding 1000-fold) enhance ( ~ 2-fold) relative conventional nano/microcrystals catalyst one-pot reactor. diffusion-programed strategy represents robust solution surmount constraints imposed by bulk marking advancement design catalyst-driven reactions.

Язык: Английский

---

Porous Adsorption Materials for Carbon Dioxide Capture in Industrial Flue Gas

Frontiers in Chemistry, Год журнала: 2022, Номер 10

Опубликована: Июнь 29, 2022

Due to the intensification of greenhouse effect and emphasis on utilization CO2 resources, enrichment separation have become a current research focus in environment energy. Compared with other technologies, pressure swing adsorption has advantages low cost high efficiency been widely used. The design preparation high-efficiency adsorbents is core technology. Therefore, high-performance porous materials attracted increasing attention. Porous specific surface area, capacity, regeneration energy, good cycle performance, moisture resistance focused on. This article summarizes optimization by then applies them field adsorption. internal laws between pore structure, chemistry, performance adsorbent are discussed. Further development requirements for treatment industrial waste gas prospected. structural carbon still focus. With applications environmental conditions, integrity, mechanical strength water need be met.

Язык: Английский

---

Surface science approach to the heterogeneous cycloaddition of CO2 to epoxides catalyzed by site-isolated metal complexes and single atoms: a review

Green Chemical Engineering, Год журнала: 2022, Номер 3(3), С. 210 - 227

Опубликована: Фев. 5, 2022

The cycloaddition of CO2 to epoxides afford cyclic organic carbonates is an increasingly relevant non-reductive strategy convert useful products able serve as high-boiling solvents, chemical intermediates, and monomers for the preparation more sustainable polymers. development efficient robust heterogeneous catalysts such transformation is, therefore, crucial can be carried out by several strategies that often require sophisticated and/or expensive networks, linkers, or compounds. A different approach CO2-epoxide coupling applying surface science methodologies graft molecular fragments single atoms on various supports leading well-defined active sites. In this context, organometallic chemistry (SOMC), along with comparable methodologies, a valuable efficient, single-site Lewis acids target reaction metal oxides, whereas, other grafting applied prepare analogous kinds surfaces. Finally, we discuss very recent advances in application atom towards highly epoxides. Overall, show prepared facile hold significant potential future synthesis from CO2.

Язык: Английский

---