Heteroatom (N or N‐S)‐Doping Induced Layered and Honeycomb Microstructures of Porous Carbons for CO2 Capture and Energy Applications

Increasing global challenges such as climate change, environmental pollution, and energy shortage have stimulated the worldwide explorations into novel and clean materials for their applications in the capture of carbon dioxide, a major greenhouse gas, and toxic pollutants, energy conversion, and storage. In this study, two microstructured carbons, namely N‐doped pillaring layered carbon (NC) and N, S codoped honeycomb carbon (NSC), have been fabricated through a one‐pot pyrolysis process of a mixture containing glucose, sodium bicarbonate, and urea or thiourea. The heteroatom doping is found to induce tailored microstructures featuring highly interconnected pore frameworks, high sp²‐C ratios, and high surface areas. The formation mechanism of the varying pore frameworks is believed to be hydrogen‐bond interactions. NSC displays a similar CO₂ adsorption capacity (4.7 mmol g^?1 at 0 °C), a better CO₂/N₂ selectivity, and higher activity in oxygen reduction reaction as compared with NC‐3 (the NC sample with the highest N content of 7.3%). NSC favors an efficient four‐electron reduction pathway and presents better methanol tolerance than Pt/C in alkaline media. The porous carbons also exhibit excellent rate performance as supercapacitors.     

Ultra‐High Surface Area Nitrogen‐Doped Carbon Aerogels Derived From a Schiff‐Base Porous Organic Polymer Aerogel for CO2 Storage and Supercapacitors

Nitrogen‐doped carbon aerogels (NCAs) have received great attention for a wide range of applications, from thermal electronics to waste water purification, heavy metal or gas adsorption, energy storage, and catalyst supports. Herein NCAs are developed via the synthesis of a Schiff‐base porous organic polymer aerogel followed by pyrolysis. By controlling the pyrolysis temperature, the polymer aerogel can be simply converted into porous NCAs with a low bulk density (5 mg cm^?3), high surface area (2356 m² g^?1), and high bulk porosity (70%). The NCAs containing 1.8–5.3 wt% N atoms exhibit remarkable CO₂ uptake capacities (6.1 mmol g^?1 at 273 K and 1 bar, 33.1 mmol g^?1 at 323 K and 30 bar) and high ideal adsorption solution theory selectivity (47.8) at ambient pressure. Supercapacitors fabricated with NCAs display high specific capacitance (300 F g^?1 at 0.5 A g^?1), fast rate (charge to 221 F g^?1 within only 17 s), and high stability (retained >98% capacity after 5000 cycles). Asymmetric supercapacitors assembled with NCAs also show high energy density and power density with maximal values of 30.5 Wh kg^?1 and 7088 W kg^?1, respectively. The outstanding CO₂ uptake and energy storage abilities are attributed to the ultra‐high surface area, N‐doping, conductivity, and rigidity of NCA frameworks.     

Porous Carbons: Structure‐Oriented Design and Versatile Applications

Porous carbon materials have demonstrated exceptional performance in a variety of energy‐ and environment‐related applications. Over the past decades, tremendous efforts have been made in the coordinated design and fabrication of porous carbon nanoarchitectures in terms of pore sizes, surface chemistry, and structure. Herein, structure‐oriented carbon design and applications are reviewed. The unique properties of porous carbon materials that offer them promising design opportunities and broad applicability in some representative fields, including water remediation, CO₂ capture, lithium‐ion batteries, lithium–sulfur batteries, lithium metal anodes, Na‐ion batteries, K‐ion batteries, supercapacitors, and the oxygen reduction reaction are highlighted. Then, the most up‐to‐date strategies for structural control and functionalization of porous carbons are summarized, toward tailoring microporous, mesoporous, macroporous, and hierarchically porous carbons with disordered or ordered, amorphous or graphitic structures. Meanwhile, the emerging features of these structures in various applications are introduced where applicable. Finally, insights into the challenges and perspectives for future development are provided.     

Identifying Active Sites of Nitrogen‐Doped Carbon Materials for the CO2 Reduction Reaction

Nitrogen‐doped carbon materials are proposed as promising electrocatalysts for the carbon dioxide reduction reaction (CRR), which is essential for renewable energy conversion and environmental remediation. Unfortunately, the unclear cognition on the CRR active site (or sites) hinders further development of high‐performance electrocatalysts. Herein, a series of 3D nitrogen‐doped graphene nanoribbon networks (N‐GRW) with tunable nitrogen dopants are designed to unravel the site‐dependent CRR activity/selectivity. The N‐GRW catalyst exhibits superior CO₂ electrochemical reduction activity, reaching a specific current of 15.4 A g_catalyst^?1 with CO Faradaic efficiency of 87.6% at a mild overpotential of 0.49 V. Based on X‐ray photoelectron spectroscopy measurements, it is experimentally demonstrated that the pyridinic N site in N‐GRW serves as the active site for CRR. In addition, the Gibbs free energy calculated by density functional theory further illustrates the pyridinic N as a more favorable site for the CO₂ adsorption, *COOH formation, and *CO removal in CO₂ reduction.     

Tunable Photodynamic Switching of DArE@PAF‐1 for Carbon Capture

A new type of photodynamic carbon capture material with up to 26 wt% CO₂ desorption capacity is synthesized via incorporation of diarylethene (DArE) as guest molecules in porous aromatic framework‐1 (PAF‐1). In these host–guest complexes, the carboxylic acid groups featured in DArE allow multiple noncovalent interactions to exist. DArE loadings ranging from 1 to 50 wt% are incorporated in PAF‐1 and the complexes characterized by UV–vis spectroscopy, FT‐IR spectroscopy, CO₂, and N₂ adsorption. Successful inclusion of DArE in PAF‐1 is indicated by the reduction of pore size distributions and an optimum loading of 5 wt% is determined by comparing the percentage photo­response and CO₂ uptake capacity at 1 bar. Mechanistic studies suggest that photoswitching modulates the binding affinity between DArE and CO₂ toward the host, triggering carbon capture and release. This is the first known example of photodynamic carbon capture and release in a PAF.     

CO2-Based Dual-Tone Resists for Electron Beam Lithography

The increasing global environmental and energy crisis has urgently motivated the advancement of sustainable materials. Significant effort has been focused on developing new materials to replace the fossil-based resists in the semiconductor industry based on greener sources such as ice, dry ice, small organic molecules, and proteins. Such resist materials, however, have yet to meet the stringent requirements of high sensitivity, high resolution, reliable repeatability, and good compatibility with the current protocols. To this end, CO₂-based polycarbonates (CO₂-PCs) obtained from the copolymerization of CO₂ and epoxides are demonstrated as sustainable dual-tone (positive & negative tone) resists for electron beam lithography. By adjusting the chemical structure, developing agent, and molecular weight, the CO₂-PCs present high sensitivities to electron beam (1.3/120 µ C cm⁻²), narrow critical dimensions (29/58 nm), and moderate line edge roughness (4.6/26.7 nm) for negative and positive resists, respectively. A deep understanding of the exposure mechanism of CO₂-PC resists is provided on the basis of the Fourier transform infrared, Raman, and electron ionization mass spectroscopy. 2D photonic crystal devices are fabricated using the negative and positive CO₂-PC resists, respectively, and both devices show distinct colors derived from their well-defined nanostructures, indicating the great practical potential of CO₂-derived electron beam resists.     

High‐Performance CO2 Capture through Polymer‐Based Ultrathin Membranes

Thin film composite (TFC) membranes have attracted great research interest for a wide range of separation processes owing to their potential to achieve excellent permeance. However, it still remains challenging to fully exploit the superiority of thin selective layers when mitigating the pore intrusion phenomenon. Herein, a facile and generic interface‐decoration‐layer strategy collaborating with molecular‐scale organic–inorganic hybridization in the selective layer to obtain a high‐performance ultrathin film composite (UTFC) membrane for CO₂ capture is reported. The interface‐decoration layer of copper hydroxide nanofibers (CHNs) enables the formation of an ultrathin selective layer (≈100 nm), achieving a 2.5‐fold increase in gas permeance. The organic part in the molecular‐scale hybrid material contributes to facilitating CO₂‐selective adsorption while the inorganic part assists in maintaining robust membrane structure, thus remarkably improving the selectivity toward CO₂. As a result, the as‐prepared membrane shows a high CO₂ permeance of 2860 GPU, superior to state‐of‐the‐art polymer membranes, with a CO₂/N₂ selectivity of 28.2. The synergistic strategy proposed here can be extended to a wide range of polymers, holding great potential to produce high‐efficiency ultrathin membranes for molecular separation.     

Polypyrrole‐Derived Activated Carbons for High‐Performance Electrical Double‐Layer Capacitors with Ionic Liquid Electrolyte

As electrical energy storage and delivery devices, carbon‐based electrical double‐layer capacitors (EDLCs) have attracted much attention for advancing the energy‐efficient economy. Conventional methods for activated carbon (AC) synthesis offer limited control of their surface area and porosity, which results in a typical specific capacitance of 70–120 F g^?1 in commercial EDLCs based on organic electrolytes and ionic liquids (ILs). Additionally, typical ACs produced from natural precursors suffer from the significant variation of their properties, which is detrimental for EDLC use in automotive applications. A novel method for AC synthesis for EDLCs is proposed. This method is based on direct activation of synthetic polymers. The proposed procedure allowed us to produce ACs with ultrahigh specific surface area of up to 3432 m² g^?1 and volume of 0.5–4 nm pores up to 2.39 cm³ g^?1. The application of the produced carbons in EDLCs based on IL electrolyte showed specific capacitance approaching 300 F g^?1, which is unprecedented for carbon materials, and 5–8% performance improvement after 10 000 charge–discharge cycles at the very high current density of 10 A g^?1. The remarkable characteristics of the produced materials and the capability of the fabricated EDLCs to operate safely in a wide electrochemical window at elevated temperatures, suggest that the proposed synthesis route offers excellent potential for large‐scale material production for EDLC use in electric vehicles and industrial applications.     

A Controllable Synthesis of Rich Nitrogen‐Doped Ordered Mesoporous Carbon for CO2 Capture and Supercapacitors

A controllable one‐pot method to synthesize N‐doped ordered mesoporous carbons (NMC) with a high N content by using dicyandiamide as a nitrogen source via an evaporation‐induced self‐assembly process is reported. In this synthesis, resol molecules can bridge the Pluronic F127 template and dicyandiamide via hydrogen bonding and electrostatic interactions. During thermosetting at 100 °C for formation of rigid phenolic resin and subsequent pyrolysis at 600 °C for carbonization, dicyandiamide provides closed N species while resol can form a stable framework, thus ensuring the successful synthesis of ordered N‐doped mesoporous carbon. The obtained N‐doped ordered mesoporous carbons possess tunable mesostructures (p6m and Im m symmetry) and pore size (3.1–17.6 nm), high surface area (494–586 m² g^?1), and high N content (up to 13.1 wt%). Ascribed to the unique feature of large surface area and high N contents, NMC materials show high CO₂ capture of 2.8–3.2 mmol g^?1 at 298 K and 1.0 bar, and exhibit good performance as the supercapacitor electrode with specific capacitances of 262 F g^?1 (in 1 M H₂SO₄) and 227 F g^?1 (in 6 M KOH) at a current density of 0.2 A g^?1.     

Polysaccharide‐Derived Carbons for Polar Analyte Separations

Highly mesoporous (Brunauer–Emmett–Teller surface area, S_BET > 200 m² g^?1; mesopore volume > 1 cm³ g^?1) carbonaceous materials are prepared in a truly sustainable manner, from the naturally occurring polysaccharide alginic acid. This approach yields large mesoporous materials (pore diameter > 14 nm) significantly without the use of a template or carbonization catalyst. The direct thermal decomposition of mesoporous forms of the acidic polysaccharide allows for an extremely flexible material preparation strategy. Materials can be prepared at any desired carbonization temperature (e.g., 200–1000 °C), possessing similar textural properties, but progressively presenting more uniform surface functionality through this temperature range, from more oxygenated surfaces at low temperatures to increasingly aromatic/graphitic‐like surfaces. The high‐temperature material (i.e., 1000 °C), while predominantly amorphous, presents some short range (turbostratic) ordering, providing sufficiently polarizable surfaces on which to perform challenging liquid phase separations of polar sugar analytes.     

Bottom‐Up Preparation of Fully sp2‐Bonded Porous Carbons with High Photoactivities

Porous carbons, possessing exceptional stability, high surface area, and electric conductivity, are broadly used as superior adsorbent, supporter, or electrode material for environmental protection, industrial catalysis, and energy storage and conversion. The construction of such kinds of materials with designable structures and properties will extremely extend their potential applications, but remains a huge synthetic challenge. Herein, a bottom‐up approach is presented to synthesize one type of fully sp² carbon–bonded frameworks by transition metal–catalyzed cross‐coupling of different polyphenylenes with electron‐withdrawing 9,9′‐bifluorenylidene (9,9′‐BF) through its 2,7‐position. The resulting porous polymeric carbons exhibit substantial semiconducting properties, such as strong light‐harvesting capabilities in the visible light region, likely due to their π‐extended backbones with donor–acceptor characters. Their electronic and porous structures can be finely tuned via the polyphenylene spacers. The intriguing properties allow these porous carbons to efficiently catalyze dye degradation under visible light or even natural sunlight with high reusability. Meanwhile, associated with their intrinsic structures, these porous carbons also exhibit highly selective degradation activities toward different dyes. In particular, the photodegradation mechanism involving oxygen and electron is elucidated for the first time for such kinds of materials, related to the presence of specific 9,9′‐BF units in their π‐conjugated skeletons.     

N-Containing Carbons Derived from Microporous Coordination Polymers for Use in Post-Combustion Flue Gas Capture

Herein, novel carbons that, owing to a high density of micropores (up to 79%) and N-content (up to 14.9%), offering exciting potential for post-combustion CO₂ capture are reported. Given that little is known about how starting materials impact the structure and performance of carbons, three different microporous materials are pyrolyzed. These include a Co-(metal-organic framework) (MOF), a Co-MOF-polymer composite, and a coordination polymer derived from the same monomer and cobalt ions. Notably, the cobalt, which is required to drive the polymerization, is subsequently leached from the carbons via acid for its reuse in MOF synthesis. Next, various metrics including CO₂ capacity, selectivity, isosteric heat of adsorption, breakthrough time and cyclability are assessed. The acid treated carbons adsorb 0.21, 0.99, and 1.11 mmol CO₂ g⁻¹, respectively, (313 K, 0.15 bar) with CO₂/N₂ selectivity ranging from 37 to 52. Due to superior capacity, the polymer-derived carbons also reveal impressive breakthrough times in simulated flue gas mixtures (15% CO₂/85% N₂, 80% RH, 313 K) ranging from 33 to 40 min g⁻¹. Similar performance is also observed under dry conditions and after pre-saturation with water for 1.5 h. Remarkably, no loss in working capacity is observed after 100 CO₂ TSA cycles (313 K/393 K).     

Deriving Efficient Porous Heteroatom‐Doped Carbon Electrocatalysts for Hydrazine Oxidation from Transition Metal Ions‐Coordinated Casein

In this work, the synthesis of high‐performance, metal ion‐imprinted, mesoporous carbon electrocatalysts for hydrazine oxidation reaction (HzOR) using casein or a family of phosphoproteins derived from cow's milk as a precursor is shown. The synthesis is made possible by mixing trace amounts of non‐noble metal ions (Fe³⁺ or Co²⁺) with casein and then producing different metal ions‐functionalized casein intermediates, which upon carbonization, followed by acid treatment, lead to metal ion‐imprinted catalytically active sites on the materials. The materials effectively electrocatalyze HzOR with low overpotentials at neutral pH and exhibit among the highest electrocatalytic performances ever reported for carbon catalysts. Their catalytic activities are also better than the corresponding control material, synthesized by carbonization of pure casein and other materials previously reported for HzOR. This work demonstrates a novel synthetic route that transforms an inexpensive protein to highly active carbon‐based electrocatalysts by modifying its surfaces with trace amounts of non‐noble metals. The types of metal ions employed in the synthesis are found to dictate the electrocatalytic activities of the materials. Notably, Fe³⁺ is found to be more effective than Co²⁺ in helping the conversion of casein into more electrocatalytically active carbon materials for HzOR.     

Nitrogen‐Doped Carbon Networks for High Energy Density Supercapacitors Derived from Polyaniline Coated Bacterial Cellulose

Bacterial cellulose (BC) is used as both template and precursor for the synthesis of nitrogen‐doped carbon networks through the carbonization of polyaniline (PANI) coated BC. The as‐obtained carbon networks can act not only as support for obtaining high capacitance electrode materials such as activated carbon (AC) and carbon/MnO₂ hybrid material, but also as conductive networks to integrate active electrode materials. As a result, the as‐assembled AC//carbon‐MnO₂ asymmetric supercapacitor exhibits a considerably high energy density of 63 Wh kg^?1 in 1.0 m Na₂SO₄ aqueous solution, higher than most reported AC//MnO₂ asymmetric supercapacitors. More importantly, this asymmetric supercapacitor also exhibits an excellent cycling performance with 92% specific capacitance retention after 5000 cycles. Those results offer a low‐cost, eco‐friendly design of electrode materials for high‐performance supercapacitors.     

Highly Efficient Electrocatalysts for Oxygen Reduction Reaction Based on 1D Ternary Doped Porous Carbons Derived from Carbon Nanotube Directed Conjugated Microporous Polymers

One‐dimensional (1D) porous materials have shown great potential for gas storage and separation, sensing, energy storage, and conversion. However, the controlled approach for preparation of 1D porous materials, especially porous organic materials, still remains a great challenge due to the poor dispersibility and solution processability of the porous materials. Here, carbon nanotube (CNT) templated 1D conjugated microporous polymers (CMPs) are prepared using a layer‐by‐layer method. As‐prepared CMPs possess high specific surface areas of up to 623 m² g^?1 and exhibit strong electronic interactions between p‐type CMPs and n‐type CNTs. The CMPs are used as precursors to produce heteroatom‐doped 1D porous carbons through direct pyrolysis. As‐produced ternary heteroatom‐doped (B/N/S) 1D porous carbons possess high specific surface areas of up to 750 m² g^?1, hierarchical porous structures, and excellent electrochemical‐catalytic performance for oxygen reduction reaction. Both of the diffusion‐limited current density (4.4 mA cm^?2) and electron transfer number (n = 3.8) for three‐layered 1D porous carbons are superior to those for random 1D porous carbon. These results demonstrate that layered and core–shell type 1D CMPs and related heteroatom‐doped 1D porous carbons can be rationally designed and controlled prepared for high performance energy‐related applications.     

Low‐Cost Chitosan‐Derived N‐Doped Carbons Boost Electrocatalytic Activity of Multiwall Carbon Nanotubes

An effective strategy is proposed to enhance the oxygen reduction reaction (ORR) performance of multiwall carbon nanotubes (MWCNTs) in both acid and alkaline electrolytes by coating them with a layer of biomass derivative N‐doped hydrothermal carbons. The N‐doped amorphous carbon coating plays triple roles: it (i) promotes the assembly of MWCNTs into a 3D network therefore improving the mass transfer and thus increasing the catalytic activity; (ii) protects the Fe‐containing active sites, present on the surface of the MWCNTs, from H₂O₂ poisoning; (iii) creates nitrogenated active sites and hence further enhances ORR activity and robustness.     

Three‐Dimensionally Ordered Macroporous Polymeric Materials by Colloidal Crystal Templating for Reversible CO2 Capture

The design and preparation of porous materials with controlled structures and functionalities is crucial to a variety of absorption‐ or separation‐relevant applications, including CO₂ capture. Here, novel functional polymeric materials with three‐dimensionally ordered macroporous (3DOM) structures are prepared by using colloidal crystals as templates using relatively simple, rapid, and inexpensive approaches. These ordered structures are used for the reversible CO₂ capture from ambient air by humidity swing. Typically, the colloidal crystal template is synthesized from polymer latex particles of poly(methyl methacrylate) (PMMA) or polystyrene (PS). To maintain the functionality of the material, it is important to prevent the porous structure collapsing, which can occur by the hydrolysis of the ester bonds in conventional crosslinkers under basic conditions. This hydrolysis can be prevented by using a water‐soluble crosslinker containing two quaternary ammonium moieties, which can be used to prepare stable porous crosslinked polymers with the monomer (vinylbenzyl)trimethylammonium chloride (VBTMACl) and using a PMMA‐based colloidal crystal template. The hydroxide‐containing monomer and dicationic crosslinker are synthesized from their chloride precursors, avoiding the ion‐exchange step which causes shrinkage of the pores. An analysis of different methods for infiltrating the monomer solution into the colloidal crystal template shows that infiltration using capillary forces leads to fewer defects than infiltration under a partial vacuum. In addition, functional macroporous films with micrometer thickness are prepared from a template of PS‐based colloidal crystals in a thin film. In general, the colloidal crystal templated materials showed improved CO₂ absorption/desorption rates and swing sizes compared to a commercially available material with similar functional groups. This work could easily be extended to create a new generation of ordered macroporous polymeric materials with tunable functionalities for other applications.     

Carbide‐Derived Carbons – From Porous Networks to Nanotubes and Graphene

Carbide‐derived carbons (CDCs) are a large family of carbon materials derived from carbide precursors that are transformed into pure carbon via physical (e.g., thermal decomposition) or chemical (e.g., halogenation) processes. Structurally, CDC ranges from amorphous carbon to graphite, carbon nanotubes or graphene. For halogenated carbides, a high level of control over the resulting amorphous porous carbon structure is possible by changing the synthesis conditions and carbide precursor. The large number of resulting carbon structures and their tunability enables a wide range of applications, from tribological coatings for ceramics, or selective sorbents, to gas and electrical energy storage. In particular, the application of CDC in supercapacitors has recently attracted much attention. This review paper summarizes key aspects of CDC synthesis, properties, and applications. It is shown that the CDC structure and properties are sensitive to changes of the synthesis parameters. Understanding of processing–structure–properties relationships facilitates tuning of the carbon material to the requirements of a certain application.