Porous Organic Polymers for Post‐Combustion Carbon Capture

One of the most pressing environmental concerns of our age is the escalating level of atmospheric CO₂. Intensive efforts have been made to investigate advanced porous materials, especially porous organic polymers (POPs), as one type of the most promising candidates for carbon capture due to their extremely high porosity, structural diversity, and physicochemical stability. This review provides a critical and in‐depth analysis of recent POP research as it pertains to carbon capture. The definitions and terminologies commonly used to evaluate the performance of POPs for carbon capture, including CO₂ capacity, enthalpy, selectivity, and regeneration strategies, are summarized. A detailed correlation study between the structural and chemical features of POPs and their adsorption capacities is discussed, mainly focusing on the physical interactions and chemical reactions. Finally, a concise outlook for utilizing POPs for carbon capture is discussed, noting areas in which further work is needed to develop the next‐generation POPs for practical applications.     

Solvent‐Induced Self‐Assembly Strategy to Synthesize Well‐Defined Hierarchically Porous Polymers

Porous polymers with well‐orchestrated nanomorphologies are useful in many fields, but high surface area, hierarchical structure, and ordered pores are difficult to be satisfied in one polymer simultaneously. Herein, a solvent‐induced self‐assembly strategy to synthesize hierarchical porous polymers with tunable morphology, mesoporous structure, and microporous pore wall is reported. The poly(ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymer micelles are cross‐linked via Friedel–Crafts reaction, which is a new way to anchor micelles into porous polymers with well‐defined structure. Varying the polarity of the solvent has a dramatic effect upon the oleophobic/oleophylic interaction, and the self‐assembly structure of PEO‐b‐PS can be tailored from aggregated nanoparticles to hollow spheres even mesoporous bulk. A morphological phase diagram is accomplished to systematically evaluate the influence of the composition of PEO‐b‐PS and the mixed solvent component on the pore structure and morphology of products. The hypercrosslinked hollow polymer spheres provide a confined microenvironment for the in situ reduction of K₂PdCl₄ to ultrasmall Pd nanoparticles, which exhibit excellent catalytic performance in solvent‐free catalytic oxidation of hydrocarbons and alcohols.     

Heteroatom‐Containing Porous Carbons Derived from Ionic Liquid‐Doped Alkali Organic Salts for Supercapacitors

A simple strategy for the synthesis of heteroatom‐doped porous carbon materials (CMs) via using ionic liquid (IL)‐doped alkali organic salts as small molecular precursors is developed. Doping of alkali organic salts (such as sodium glutamate, sodium tartrate, and sodium citrate) with heteroatoms containing ILs (including 1‐butyl‐3‐methylimidazolium chlorine and 3‐butyl‐4‐methythiazolebromination) not only incorporates the heteroatoms into the carbon frameworks but also highly improves the carbonization yield, as compared with that of either alkali organic salts or ILs as precursors. The porous structure of CMs can be tuned by adjusting the feed ratio of ILs. The porous CMs derived from 1‐butyl‐3‐methylimidazolium chlorine‐doped sodium glutamate exhibit high charge storage capacity with a specific capacitance of 287 F g^?1 and good stability over 5000 cycles in 6 m KOH at a current density of 1 A g^?1 for supercapacitors. This strategy opens a simple and efficient method for the synthesis of heteroatom‐doped porous CMs.     

Polyimide@Ketjenblack Composite: A Porous Organic Cathode for Fast Rechargeable Potassium‐Ion Batteries

Potassium‐ion batteries (PIBs) configurated by organic electrodes have been identified as a promising alternative to lithium‐ion batteries. Here, a porous organic Polyimide@Ketjenblack is demonstrated in PIBs as a cathode, which exhibits excellent performance with a large reversible capacity (143 mAh g^?1 at 100 mA g^?1), high rate capability (125 and 105 mAh g^?1 at 1000 and 5000 mA g^?1), and long cycling stability (76% capacity retention at 2000 mA g^?1 over 1000 cycles). The domination of fast capacitive‐like reaction kinetics is verified, which benefits from the porous structure synthesized using in situ polymerization. Moreover, a renewable and low‐cost full cell is demonstrated with superior rate behavior (106 mAh g^?1 at 3200 mA g^?1). This work proposes a strategy to design polymer electrodes for high‐performance organic PIBs.     

Poly(3,4‐alkylenedioxypyrroles): The PXDOPs as Versatile Yet Underutilized Electroactive and Conducting Polymers

The poly(3,4‐dioxypyrrole) (PXDOP) family of conducting and electroactive polymers has now been developed to the point that multiple synthetic routes allow many functionalized polymers with controllable optoelectronic and redox properties. These properties, which include high conductivity, multicolor cathodic and anodic electrochromism, and rapid redox switching, allow these materials to be used in a variety of applications that potentially include conducting coatings, electrochromic windows and displays, chemical sensors, bioactive materials, and mechanical actuators. Surprisingly, the scientific literature published on the PXDOP derivatives has been isolated and sparse compared to that of other conducting polymers. This report will highlight the synthesis and materials properties of PXDOPs and show how these powerful materials fit into the frontier of conducting polymers research.     

Wide‐Range Tuning and Enhancement of Organic Long‐Persistent Luminescence Using Emitter Dopants

Most long‐persistent luminescent (LPL) materials, which slowly release energy absorbed from ambient light, are based on inorganic compounds. Organic long‐persistent luminescent (OLPL) systems have advantages over inorganic LPL materials in terms of solubility, transparency, and flexibility. Here, the characteristics of OLPL emission are improved by doping emitter molecules into an OLPL matrix. Greenish‐blue to red and even warm white emission are achieved by energy transfer from exciplex in the OLPL matrix to the emitter dopants. The dopants also improve brightness and emission duration through efficient radiative decay and the trapping of electrons, respectively. This technique will enable the development of a wide range of organic glow‐in‐the‐dark paints.     

Polymer Microstructures through Two‐Photon Crosslinking

Two‐photon crosslinking of polymers (2PC) is proposed as a novel method for the fabrication of freestanding microstructures via two‐photon lithography. During this process in the confocal volume, two‐photon absorption leads to (formal) C,H‐insertion reactions, and consequently to a strictly localized crosslinking of the polymer. To achieve this, the polymer is coated as a solvent‐free (glassy) film onto an appropriate substrate, and the desired microstructure is written by 2PC into this glass. In all regions outside of the focal volume where no two‐photon process occurs, the polymer remains uncrosslinked and can be washed away during a developing process. Using a self‐assembled monolayer containing the same photoreactive group allows covalent attachment of the forming freestanding structures to the substrate, and thus guarantees an improved stability of these structures against shear‐induced detachment. As the two photon process is carried out in the glassy state, in a simple way, multilayer structures can be used to write structures having a varying chemical composition perpendicular to the surface. As an example, the 2PC process is used to build a structure from both protein‐repellent and protein‐adsorbing polymers so that the resulting 3D structure exhibits spatially controlled protein adsorption.     

Porous Polymers as Multifunctional Material Platforms toward Task‐Specific Applications

Exploring advanced porous materials is of critical importance in the development of science and technology. Porous polymers, being famous for their all‐organic components, tailored pore structures, and adjustable chemical components, have attracted an increasing level of research interest in a large number of applications, including gas adsorption/storage, separation, catalysis, environmental remediation, energy, optoelectronics, and health. Recent years have witnessed tremendous research breakthroughs in these fields thanks to the unique pore structures and versatile skeletons of porous polymers. Here, recent milestones in the diverse applications of porous polymers are presented, with an emphasis on the structural requirements or parameters that dominate their properties and functionalities. The Review covers the following applications: i) gas adsorption, ii) water treatment, iii) separation, iv) heterogeneous catalysis, v) electrochemical energy storage, vi) precursors for porous carbons, and vii) other applications (e.g., intelligent temperature control textiles, sensing, proton conduction, biomedicine, optoelectronics, and actuators). The key requirements for each application are discussed and an in‐depth understanding of the structure–property relationships of these advanced materials is provided. Finally, a perspective on the future research directions and challenges in this field is presented for further studies.     

Achieving Persistent,Efficient, and Robust Room‐Temperature Phosphorescence from Pure Organics for Versatile Applications

Pure organic persistent room‐temperature phosphorescence (p‐RTP) under ambient conditions is attractive but challenging due to the slow intersystem crossing process and susceptibility of triplet excitons. Fabrication of pure organic RTP luminogens with simultaneously high efficiency and ultralong lifetime still remains a daunting job, owing to their conflicting requirements for the T₁ nature of (n,π*) and (π,π*) characteristics, respectively. Herein, a group of amide‐based derivatives with efficient p‐RTP is developed through the incorporation of spin–orbital‐coupling‐promoting groups of carbonyl and aromatic π units, giving impressive p‐RTP with lifetime and efficiency of up to 710.6 ms and 10.2%, respectively. Furthermore, two of the luminogens demonstrate intense p‐RTP after vigorous mechanical stimulation, indicating their robust nature, which is rarely encountered. Efficient and robust p‐RTP even in the amorphous state endows them promising potential for encryption and bioimaging with facile fabrication processes. A bioimaging study with live mice indicates that such highly robust p‐RTP is tremendously beneficial for in vivo afterglow imaging with an ultrahigh signal‐to‐background ratio of 428. These results strongly imply the possibility of realizing efficient and robust p‐RTP from pure organics even without meticulous protection, thus paving the way to their promising and versatile applications.     

Thermally Stable Metal‐Organic Framework‐Templated Synthesis of Hierarchically Porous Metal Sulfides: Enhanced Photocatalytic Hydrogen Production

Porous nanostructured materials are demonstrated to be very promising in catalysis due to their well accessible active sites. Thermally stable metal‐organic frameworks (MOFs) as hard templates are successfully utilized to afford porous metal oxides and subsequently metal sulfides by a nanocasting method. The resultant metal oxides/sulfides show considerable Brunauer–Emmett–Teller (BET) surface areas, by partially inheriting the pore character of MOF templates. Preliminary investigation on the obtained hierarchically porous CdS for water splitting, as a proof of concept, demonstrates its much higher activity than both corresponding bulk and nanosized counterparts, under visible light irradiation. Given the structural diversity and tailorability of MOFs, such synthetic approach may open an avenue to the synthesis of advanced porous materials for functional applications.     

Nanoarchitectured Design of Porous Materials and Nanocomposites from Metal‐Organic Frameworks

The emergence of metal‐organic frameworks (MOFs) as a new class of crystalline porous materials is attracting considerable attention in many fields such as catalysis, energy storage and conversion, sensors, and environmental remediation due to their controllable composition, structure and pore size. MOFs are versatile precursors for the preparation of various forms of nanomaterials as well as new multifunctional nanocomposites/hybrids, which exhibit superior functional properties compared to the individual components assembling the composites. This review provides an overview of recent developments achieved in the fabrication of porous MOF‐derived nanostructures including carbons, metal oxides, metal chalcogenides (metal sulfides and selenides), metal carbides, metal phosphides and their composites. Finally, the challenges and future trends and prospects associated with the development of MOF‐derived nanomaterials are also examined.     

Micro‐Blooming: Hierarchically Porous Nitrogen‐Doped Carbon Flowers Derived from Metal‐Organic Mesocrystals

Synthesis of 3D flower‐like zinc‐nitrilotriacetic acid (ZnNTA) mesocrystals and their conformal transformation to hierarchically porous N‐doped carbon superstructures is reported. During the solvothermal reaction, 2D nanosheet primary building blocks undergo oriented attachment and mesoscale assembly forming stacked layers. The secondary nucleation and growth preferentially occurs at the edges and defects of the layers, leading to formation of 3D flower‐like mesocrystals comprised of interconnected 2D micropetals. By simply varying the pyrolysis temperature (550–1000 °C) and the removal method of in the situ‐generated Zn species, nonporous parent mesocrystals are transformed to hierarchically porous carbon flowers with controllable surface area (970–1605 m² g^?1), nitrogen content (3.4–14.1 at%), pore volume (0.95–2.19 cm³ g^?1), as well as pore diameter and structures. The carbon flowers prepared at 550 °C show high CO₂/N₂ selectivity due to the high nitrogen content and the large fraction of (ultra)micropores, which can greatly increase the CO₂ affinity. The results show that the physicochemical properties of carbons are highly dependent on the thermal transformation and associated pore formation process, rather than directly inherited from parent precursors. The present strategy demonstrates metal‐organic mesocrystals as a facile and versatile means toward 3D hierarchical carbon superstructures that are attractive for a number of potential applications.     

A Liquid‐Metal‐Enabled Versatile Organic Alkali‐Ion Battery

Despite the high specific capacity and low redox potential of alkali metals, their practical application as anodes is still limited by the inherent dendrite‐growth problem. The fusible sodium–potassium (Na–K) liquid metal alloy is an alternative that detours this drawback, but the fundamental understanding of charge transport in this binary electroactive alloy anode remains elusive. Here, comprehensive characterization, accompanied with density function theory (DFT) calculations, jointly expound the Na–K anode‐based battery working mechanism. With the organic cathode sodium rhodizonate dibasic (SR) that has negligible selectivity toward cations, the charge carrier is screened by electrolytes due to the selective ionic pathways in the solid electrolyte interphase (SEI). Stable cycling for this Na–K/SR battery is achieved with capacity retention per cycle to be 99.88% as a sodium‐ion battery (SIB) and 99.70% as a potassium‐ion battery (PIB) for over 100 cycles. Benefitting from the flexibility of the liquid metal and the specially designed carbon nanofiber (CNF)/SR layer‐by‐layer cathode, a flexible dendrite‐free alkali‐ion battery is achieved with an ultrahigh areal capacity of 2.1 mAh cm^?2. Computation‐guided materials selection, characterization‐supported mechanistic understanding, and self‐validating battery performance collectively promise the prospect of a high‐performance, dendrite‐free, and versatile organic‐based liquid metal battery.