Hydrogen-Bonded Organic Frameworks: A Rising Class of Porous Molecular Materials

Accounts of Materials Research, Год журнала: 2020, Номер 1(1), С. 77 - 87

Опубликована: Окт. 13, 2020

ConspectusHydrogen-bonded organic frameworks (HOFs) are a class of porous molecular materials that rely on the assembly building blocks by means hydrogen-bonding interactions to form two-dimensional (2D) and three-dimensional (3D) crystalline networks. The reversible nature hydrogen-bond formation endows HOFs with attributes solution processability simple regeneration. High-quality single crystals can be grown easily for unambiguous superstructure determination single-crystal X-ray diffraction, which is crucial elucidation superstructure–property relationships. During past decade, considerable progress has been achieved in realizing stable permanent porosities focusing design order introduce rigidity, auxiliary [π···π] interactions, interpenetration their sustain extended applications far-reaching, spanning catalysis, energy, biomedical products as well storage separation fine chemicals.In this Account, we, first all, provide an overview chronological development HOFs, starting from seminal work Marsh Duchamp 1969 crystal hydrogen-bonded networks trimesic acid. We identify novel motifs such diaminotriazine (DTA), introduction concept tectonics, establishment porosity being some milestones, incentivized current burgeoning research endeavors developing multifunctional materials. This Account focused primarily surveying strategies constructing 3D based peripheral carboxyl groups. These presented following categories: (1) polycatenation 2D trigonal global frameworks, (2) utilization geometries─tetrahedral prismatic─that predisposed networks, (3) docking shape-fitting geometrically labile blocks. emphasize how geometry plays important role modulating superstructures so address specific applications. Recognizing silico ultimate goal researchers field, we also discuss recent advances prediction lead supramolecular assess complications implementing computational methods complex superstructures. hope will inspire new designs creative approaches engineering aid abet customizable properties.

Язык: Английский

---

Two-Dimensional Covalent Organic Frameworks with Cobalt(II)-Phthalocyanine Sites for Efficient Electrocatalytic Carbon Dioxide Reduction

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(18), С. 7104 - 7113

Опубликована: Май 3, 2021

The rapid development in synthesis methodology and applications for covalent organic frameworks (COFs) has been witnessed recent years. However, the of highly stable functional COFs still remains a great challenge. Herein two-dimensional polyimide-linked phthalocyanine (denoted as CoPc-PI-COF-1 CoPc-PI-COF-2) have devised prepared through solvothermal reaction tetraanhydrides 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato cobalt(II) with 1,4-phenylenediamine 4,4′-biphenyldiamine, respectively. resultant CoPc-PI-COFs four-connected sql net exhibit AA stacking configurations according to powder X-ray diffraction studies, showing permanent porosity, thermal stability above 300 °C, excellent resistance 12 M HCl aqueous solution 20 days. Current–voltage curves reveal conductivity CoPc-PI-COF-2 value 3.7 × 10–3 1.6 S m–1, Due same Co(II) electroactive sites together similar porosity CO2 adsorption capacity CoPc-PI-COFs, cathodes made up carbon black display CO2-to-CO Faradaic efficiency 87–97% at applied potentials between −0.60 −0.90 V (vs RHE) 0.5 KHCO3 solution. comparison CoPc-PI-COF-2&carbon electrode, counterpart provides larger current density (jCO) −21.2 mA cm–2 associated its higher conductivity. This cathode also high turnover number frequency, amounting 277 000 2.2 s–1 −0.70 during 40 h measurement. present result clearly discloses potential 2D porous crystalline solids electrocatalysis.

Язык: Английский

---

Microporous framework membranes for precise molecule/ion separations

Chemical Society Reviews, Год журнала: 2020, Номер 50(2), С. 986 - 1029

Опубликована: Ноя. 23, 2020

Microporous framework membranes with well-defined micropore structure such as metal-organic and covalent organic hold great promise for the enormous challenging separations in energy environment fields.

Язык: Английский

---

Non-carbon-supported single-atom site catalysts for electrocatalysis

Energy & Environmental Science, Год журнала: 2021, Номер 14(5), С. 2809 - 2858

Опубликована: Янв. 1, 2021

Non-carbon supported SACs were classified into eight categories based on the nature of their substrates for first time, and corresponding anchoring stabilization mechanisms have been systematically summarized discussed.

Язык: Английский

---

Design of higher valency in covalent organic frameworks

Science, Год журнала: 2020, Номер 370(6515)

Опубликована: Окт. 22, 2020

Higher-valency ligands for COFs Metal-organic frameworks (MOFs) have exhibited more extensive connectivity (valency) and topological diversity than covalent organic (COFs), mainly because MOF linkers can connect from 3 to 24 discrete units or even infinity one-dimensional rods. For COFs, generally a valency of 4 that reflect the carbon. Gropp et al. created cubane-like 1,4-boronophenylphosphonic acid could condense make with 8 or, by adding acid, form large, single crystals an infinite-rod topology. Science , this issue p. eabd6406

Язык: Английский

---