Porous organic polymers for light-driven organic transformations

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(7), P. 2444 - 2490

Published: Jan. 1, 2022

As a new generation of porous materials, organic polymers (POPs), have recently emerged as powerful platform heterogeneous photocatalysis. POPs are constructed using extensive synthesis methodologies, with various functional units being connected via high-energy covalent bonds. This review systematically presents the recent advances in for visible-light driven transformations. Herein, we firstly summarize common construction strategies POP-based photocatalysts based on two major approaches: pre-design and post-modification; secondly, categorize methods reaction types constructing POPs. We then classify introduce specific reactions current light-driven POP-mediated Finally, outline state development problems faced transformations by POPs, present some perspectives to motivate reader explore solutions these confront challenges process.

Language: Английский

---

Metal-organic framework nanocrystal-derived hollow porous materials: Synthetic strategies and emerging applications

The Innovation, Journal Year: 2022, Volume and Issue: 3(5), P. 100281 - 100281

Published: July 6, 2022

Language: Английский

---

Bioinspired Framework Catalysts: From Enzyme Immobilization to Biomimetic Catalysis

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(9), P. 5347 - 5420

Published: April 12, 2023

Enzymatic catalysis has fueled considerable interest from chemists due to its high efficiency and selectivity. However, the structural complexity vulnerability hamper application potentials of enzymes. Driven by practical demand for chemical conversion, there is a long-sought quest bioinspired catalysts reproducing even surpassing functions natural As nanoporous materials with surface areas crystallinity, metal-organic frameworks (MOFs) represent an exquisite case how enzymes their active sites are integrated into porous solids, affording heterogeneous superior stability customizable structures. In this review, we comprehensively summarize advances MOFs catalysis, discuss design principle various MOF-based catalysts, such as MOF-enzyme composites embedded sites, explore utility these in different reactions. The advantages enzyme mimetics also highlighted, including confinement, templating effects, functionality, comparison homogeneous supramolecular catalysts. A perspective provided potential solutions addressing current challenges MOF catalysis.

Language: Английский

---

Metal organic frameworks for antibacterial applications

Chemical Engineering Journal, Journal Year: 2022, Volume and Issue: 435, P. 134975 - 134975

Published: Feb. 2, 2022

Language: Английский

---

Metal-organic frameworks for catalysis: Fundamentals and future prospects

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2023, Volume and Issue: 45, P. 1 - 5

Published: Jan. 16, 2023

Language: Английский

---

Control of selectivity in organic synthesis via heterogeneous photocatalysis under visible light

Deleted Journal, Journal Year: 2022, Volume and Issue: 1, P. e9120006 - e9120006

Published: May 12, 2022

Organic synthesis driven by heterogeneous catalysis is a central research theme to both fundamental and industrial production of fine chemicals. However, the employment stoichiometric strong oxidizing or reducing reagents (e.g., K₂Cr₂O₇ LiAlH₄) harsh reaction conditions high temperature pressure) always leads products overreaction other by-product residues salt acid waste). Thus poor control product selectivity tremendous energy consumption result in urgent demand develop novel technologies for catalysis. Given current global development CO₂ reduction sustainable utilization, one promising protocol photocatalysis. It enables solar-to-chemical conversion under mild room temperature, ambient pressure, air as oxidant) offers unique pathways improved control. To accurately tailor desired products, electronic structure positions valence-band maximum conduction-band minimum), geometric nanorod, nanosheet, porous morphology), surface chemical micro-environment vacancy sites co-catalysts) photocatalysts require rational design construction. In this review, we will briefly analyze some effective photocatalytic systems with excellent regulation ability organic transformations (mainly oxidation types) visible light irradiation, put forward opinions on optimal fabrication nanostructured realize selective synthesis.

Language: Английский

---

Linker Engineering of Sandwich‐Structured Metal–Organic Framework Composites for Optimized Photocatalytic H₂ Production

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(39)

Published: July 8, 2023

While the microenvironment around catalytic sites is recognized to be crucial in thermocatalysis, its roles photocatalysis remain subtle. In this work, a series of sandwich-structured metal-organic framework (MOF) composites, UiO-66-NH2 @Pt@UiO-66-X (X means functional groups), rationally constructed for visible-light photocatalytic H2 production. By varying ─X groups UiO-66-X shell, Pt and photosensitive core can simultaneously modulated. Significantly, MOF composites with identical light absorption loading present distinctly different production rates, following group sequence ─H > ─Br ─NA (naphthalene) ─OCH3 ─Cl ─NO2 . @Pt@UiO-66-H demonstrates rate up 2708.2 µmol g-1 h-1 , ≈222 times that @Pt@UiO-66-NO2 Mechanism investigations suggest variation balance charge separation proton reduction ability Pt, leading an optimal activity at equilibrium point.

Language: Английский

---

Electrosynthesis of α‐Amino Acids from NO and other NO_x species over CoFe alloy‐decorated Self‐standing Carbon Fiber Membranes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: May 31, 2023

Abstract The conversion of industrial exhaust gases nitrogen oxides into high‐value products is significantly meaningful for global environment and human health. And green synthesis amino acids vital biomedical research sustainable development mankind. Herein, we demonstrate an innovative approach converting nitric oxide (NO) to a series α‐amino (over 13 kinds) through electrosynthesis with α‐keto over self‐standing carbon fiber membrane CoFe alloy. essential leucine exhibits high yield 115.4 μmol h −1 corresponding Faradaic efficiency 32.4 %, gram can be obtained within 24 hours in lab as well ultra‐long stability (>240 h) the catalyst, which could convert NO NH 2 OH rapidly attacking acid subsequent hydrogenation form acid. In addition, this method also suitable other sources including gaseous or liquidus 3 − . Therefore, work not only presents promising prospects from gas nitrate‐laden waste water products, but has significant implications synthetizing catalytic science.

Language: Английский

---

Interfacial Engineering of Bimetallic Ni/Co-MOFs with H-Substituted Graphdiyne for Ammonia Electrosynthesis from Nitrate

ACS Nano, Journal Year: 2023, Volume and Issue: 17(7), P. 6687 - 6697

Published: March 17, 2023

The electrochemical synthesis of ammonia is highly dependent on the coupling reaction between nitrate and water, for which an electrocatalyst with a multifunctional interface anticipated to promote deoxygenation hydrogenation water. Herein, by engineering surface bimetallic Ni/Co-MOFs (NiCoBDC) hydrogen-substituted graphdiyne (HsGDY), hybrid nanoarray NiCoBDC@HsGDY has been achieved toward scale-up nitrate-to-ammonia conversion. On one hand, partial electron transfers from Ni2+ coordinatively unsaturated Co2+ NiCoBDC, not only promotes *NO3 but also activates water-dissociation *H Ni2+. other conformal coated HsGDY facilitates both electrons NO3- ions gathering NiCoBDC HsGDY, moves forward rate-determining step *N *H2O Co2+. As result, such delivers high NH3 yield rates Faradaic efficiency above 90% over wide potential pH windows. When assembled into galvanic Zn-NO3- battery, power density 3.66 mW cm-2 achieved, suggesting its in area aqueous Zn-based batteries.

Language: Английский

---

Construction of Three-Dimensional Dendritic Hierarchically Porous Metal–Organic Framework Nanoarchitectures via Noncentrosymmetric Pore–Induced Anisotropic Assembly

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(30), P. 16498 - 16507

Published: July 21, 2023

As a unique class of modular nanomaterials, metal-organic framework (MOF) nanoparticles have attracted widespread interest for use in various fields because their diverse chemical functionalities, intrinsic microporosity, and three-dimensional (3D) nanoarchitectures. However, endowing MOF nanomaterials with precisely controlled structural symmetries hierarchical macro/mesoporosities remains formidable challenge the researchers. Herein, we report facile noncentrosymmetric pore-induced anisotropic assembly strategy to prepare series 3D dendritic (UiO-66) highly controllable macro/meso/microporosities. The synthetic route these depends on nucleation spherical nanocones center-radial channels oriented growth isotropic nanospheres through continuous increase radius solid angle. This enables fabrication asymmetric nanostructures abundant geometries porous structures by regulating concentration amphiphilic triblock copolymer templates. Furthermore, average pore diameter resultant can be systematically manipulated wide range from 35 130 nm finely tuning reaction temperature. Meanwhile, also extended synthesize other similar architectures. Compared microporous UiO-66 nanocrystals, macro/meso/microporosities show enhanced catalytic activity CO2 cycloaddition reaction. methodology provides new insights into rational construction sophisticated open hierarchically MOFs many potential applications.

Language: Английский

---