Porous framework materials for energy&environment relevant applications:A systematic review

Carbon peaking and carbon neutralization trigger a technical revolution in energy&environment related fields.Development of new technologies for green energy production and storage,industrial energy saving and efficiency reinforcement,carbon capture,and pollutant gas treatment is in highly imperious demand.The emerging porous framework materials such as metal–organic frameworks(MOFs),covalent organic frameworks(COFs)and hydrogen-bonded organic frameworks(HOFs),owing to the permanent porosity,tremendous specific surface area,designable structure and customizable functionality,have shown great potential in major energy-consuming industrial processes,including sustainable energy gas catalytic conversion,energy-efficient industrial gas separation and storage.Herein,this manuscript presents a systematic review of porous framework materials for global and comprehensive energy&environment related applications,from a macroscopic and application perspective.

Facile preparation of Fe/N-based biomass porous carbon composite towards enhancing the thermal decomposition of DAP-4

Fe/N-based biomass porous carbon composite(Fe/N-p Carbon) was prepared by a facile high-temperature carbonization method from biomass,and the effect of Fe/N-p Carbon on the thermal decomposition of energetic molecular perovskite-based material DAP-4 was studied.Biomass porous carbonaceous materials was considered as the micro/nano support layers for in situ deposition of Fe/N precursors.Fe/Np Carbon was prepared simply by the high-temperature carbonization method.It was found that it showed the inherent catalysis properties for thermal decomposition of DAP-4.The heat release of DAP-4/Fe/N-p Carbon by DSC curves tested had increased slightly,compared from DAP-4/Fe/N-p Carbon-0.The decomposition temperature peak of DAP-4 at the presence of Fe/N-p Carbon had reduced by 79°C from384.4°C(pure DAP-4) to 305.4°C(DAP-4/Fe/N-p Carbon-3).The apparent activation energy of DAP-4thermal decomposition also had decreased by 29.1 J/mol.The possible catalytic decomposition mechanism of DAP-4 with Fe/N-p Carbon was proposed.

Biomass-derived porous carbon materials for advanced lithium sulfur batteries

Biomass, as the most widely used carbon sources, is the main ingredient in the formation of fossil fuels. Biomass-derived novel carbons(BDNCs) have attracted much attention because of its adjustable physical/chemical properties, environmentally friendliness, and considerable economic value. Nature contributes to the biomass with bizarre microstructures with micropores, mesopores or hierarchical pores.Currently, it has been confirmed that biomass has great potential applications in energy storage devices,especially in lithium-sulfur(Li–S) batteries. In this article, the synthesis and function of BDNCs for Li–S batteries are presented, and the electrochemical effects of structural diversity, porosity and surface heteroatom doping of the carbons in Li-S batteries are discussed. In addition, the economic benefits, new trends and challenges are also proposed for further design excellent BDNCs for Li–S batteries.

A Review on Metal-Organic Framework-Derived Porous Carbon-Based Novel Microwave Absorption Materials

The development of microwave absorption materials(MAMs) is a considerable important topic because our living space is crowed with electromagnetic wave which threatens human’s health.And MAMs are also used in radar stealth for protecting the weapons from being detected.Many nanomaterials were studied as MAMs,but not all of them have the satisfactory performance.Recently,metal-organic frameworks(MOFs) have attracted tremendous attention owing to their tunable chemical structures,diverse properties,large specific surface area and uniform pore distribution.MOF can transform to porous carbon(PC) which is decorated with metal species at appropriate pyrolysis temperature.However,the loss mechanism of pure MOF-derived PC is often relatively simple.In order to further improve the MA performance,the MOFs coupled with other loss materials are a widely studied method.In this review,we summarize the theories of MA,the progress of different MOF-derived PC-based MAMs,tunable chemical structures incorporated with dielectric loss or magnetic loss materials.The different MA performance and mechanisms are discussed in detail.Finally,the shortcomings,challenges and perspectives of MOF-derived PC-based MAMs are also presented.We hope this review could provide a new insight to design and fabricate MOF-derived PC-based MAMs with better fundamental understanding and practical application.

Functional porous carbon-based composite electrode materials for lithium secondary batteries

The synthetic routes of porous carbons and the applications of the functional porous carbon-based composite electrode materials for lithium secondary batteries are reviewed. The synthetic methods have made great breakthroughs to control the pore size and volume, wall thickness, surface area, and connectivity of porous carbons, which result in the development of functional porous carbon-based composite electrode materials. The effects of porous carbons on the electrochemical properties are further discussed. The porous carbons as ideal matrixes to incorporate active materials make a great improvement on the electrochemical properties because of high surface area and pore volume, excellent electronic conductivity, and strong adsorption capacity. Large numbers of the composite electrode materials have been used for the devices of electrochemical energy conversion and storage, such as lithium-ion batteries （LIBs）, Li-S batteries, and Li-O2 batteries. It is believed that functional porous carbon-based composite electrode materials will continuously contribute to the field of lithium secondary batteries.

Novel Hybrid Nanoparticles of Vanadium Nitride/Porous Carbon as an Anode Material for Symmetrical Supercapacitor

Hybrid materials of vanadium nitride and porous carbon nanoparticles(VN/PCNPs) were fabricated by a facile pyrolysis process of vanadium pentoxide(V_2O_5) xerogel and melamine at relatively low temperature of 800 °C for supercapacitor application. The effects of the feed ratio of V_2O_5 to melamine(r), and nitrogen flow rate on the microstructure and electrochemical performance were also investigated. It was found that the size of the as-synthesized nanoparticles is about 20 nm. Both r value and N_2 flow rate have enormous impacts on morphology and microstructure of the nanoparticle, which correspondingly determined the electrochemical performance of the material. The VN/C hybrid nanoparticles exhibited high capacitive properties, and a maximum specific capacitance of 255.0 Fg^(-1) was achieved at a current density of 1.0 Ag^(-1) in 2 M KOH aqueous electrolyte and the potential range from 0 to -1.15 V. In addition,symmetrical supercapacitor fabricated with the as-synthesized VN/PCNPs presents a high specific capacitance of 43.5 F g^(-1) at 0.5 A g^(-1) based on the entire cell, and an energy density of 8.0 Wh kg^(-1) when the power density was 575 W kg^(-1). Even when the power density increased to 2831.5 W kg^(-1), the energy density still remained 6.1 Wh kg^(-1).

Adsorption of phenol from aqueous solution by a hierarchical micro-nano porous carbon material

A hierarchical micro-nano porous carbon material (MNC) was prepared using expanded graphite (EG), sucrose, and phosphoric acid as raw materials, followed by sucrose-phosphoric acid solution impregnation, solidification, carbonization and activation. Nitrogen adsorption and mercury porosimetry show that mixed nanopores and micropores coexist in MNC with a high specific surface area of 1978 m2·g-1 and a total pore volume of 0.99 cm3·g-1. In addition, the MNC is found to consist of EG and activated carbon with the latter deposited on the interior and the exterior surfaces of the EG pores. The thickness of the activated carbon layer is calculated to be about one hundred nanometers and is further confirmed by scanning electron microscope (SEM) and transmission election microscope (TEM). A maximum static phenol adsorption of 241.2 mg·g-1 was obtained by using MNC, slightly higher than that of 220.4 mg·g-1 by using commercial activated carbon (CAC). The phenol adsorption kinetics were investigated and the data fitted well to a pseudo-second-order model. Also, an intra-particle diffusion mechanism was proposed. Furthermore, it is found that the dynamic adsorption capacity of MNC is nearly three times that of CAC. The results suggest that the MNC is a more efficient adsorbent than CAC for the removal of phenol from aqueous solution.

Nonlinear stability of advanced sandwich cylindrical shells comprising porous functionally graded material and carbon nanotube reinforced composite layers under elevated temperature

The nonlinear stability of sandwich cylindrical shells comprising porous functionally graded material(FGM) and carbon nanotube reinforced composite(CNTRC)layers subjected to uniform temperature rise is investigated. Two sandwich models corresponding to CNTRC and FGM face sheets are proposed. Carbon nanotubes(CNTs) in the CNTRC layer are embedded into a matrix according to functionally graded distributions. The effects of porosity in the FGM and the temperature dependence of properties of all constituent materials are considered. The effective properties of the porous FGM and CNTRC are determined by using the modified and extended versions of a linear mixture rule, respectively. The basic equations governing the stability problem of thin sandwich cylindrical shells are established within the framework of the Donnell shell theory including the von K’arm’an-Donnell nonlinearity. These equations are solved by using the multi-term analytical solutions and the Galerkin method for simply supported shells.The critical buckling temperatures and postbuckling paths are determined through an iteration procedure. The study reveals that the sandwich shell model with a CNTRC core layer and relatively thin porous FGM face sheets can have the best capacity of thermal load carrying. In addition, unlike the cases of mechanical loads, porosities have beneficial effects on the nonlinear stability of sandwich shells under the thermal load. It is suggested that an appropriate combination of advantages of FGM and CNTRC can result in optimal efficiency for advanced sandwich structures.

Millimeter-Wave Absorption Properties of Thin Wave Absorber in Free Space with New Porous Carbon Material

In this paper, we focus on PHYTOPOROUS, a porous carbon material made entirely from plant-based ingredients, as a new broadband-wave absorber material that acts in the millimeter wave band. We created prototypes of thin rubber-sheet wave absorbers that contain porous carbon (PHYTOPOROUS) made from rice chaff and soybean hulls, which are both agricultural residue products that are generated in large quantities. We investigated the permittivity and reflectance characteristics of this material using the free-space time-domain method. The thin rubber-sheet wave absorber that contained PHYTOPOROUS made from soybean hulls exhibited a frequency band that was approximately 18 GHz wide and centered at 90 GHz. The return loss for this material was greater than −20 dB. This demonstrates that the material provides nearly constant reflection absorption over a wide frequency band.

Converting furfural residue wastes to carbon materials for high performance supercapacitor

Sustainable development based on the value-added utilization of furfural residues(FRs)is an effective way to achieve a profitable circular economy.This comprehensive work highlights the potential of FRs as precursor to prepare porous carbons for high performance supercapacitors(SCs).To improve the electrochemical performance of FR-based carbon materials,a facile route based on methanol pretreatment coupled with pre-carbonization and followed KOH activation is proposed.More defects could be obtained after methanol treatment,which is incline to optimize textural structure.The activated methanol treated FR-based carbon materials(AFRMs)possess high specific surface area(1753.5 m^(2) g^(-1)),large pore volume(0.85 cm^(3) g^(-1)),interconnected micro/mesoporous structure,which endow the AFRMs with good electrochemical performance in half-cell(326.1 F g^(-1) at 0.1 Ag^(-1),189.4 Fg^(-1) at 50 A g^(-1) in 6 mol L^(-1) KOH).The constructed symmetric SCs based on KOH,KOH–K_(3)Fe(CN)_(6) and KOH-KI electrolyte deliver energy density up to 8.9,9.9 and 10.6 Wh kg^(-1) with a capacitance retention of over 86%after 10,000 cycles.Furthermore,the self-discharge can be restrained by the addition of K_(3)Fe(CN)_(6) and KI in KOH electrolyte.This study provides an effective approach for high-valued utilization of FR waste.

Rational design of new in situ reduction of Ni(II)catalytic system for low-cost and large-scale preparation of porous aromatic frameworks

Porous aromatic framework 1(PAF-1)is an extremely representative nanoporous organic framework owing to its high stability and exceptionally high surface area.Currently,the synthesis of PAF-1 is catalyzed by the Ni(COD)2/COD/bpy system,suffering from great instability and high cost.Herein,we developed an in situ reduction of the Ni(II)catalytic system to synthesize PAF-1 in low cost and high yield.The active Ni(0)species produced from the NiCl_(2)/bpy/NaI/Mg catalyst system can effectively catalyze homocoupling of tetrakis(4-bromophenyl)methane at the room temperature to form PAF-1 with high Brunauer-Emmett-Teller(BET)-specific surface area up to 4948 m^(2) g^(−1)(Langmuir surface area,6785 m2 g−1).The possible halogen exchange and dehalogenation coupling mechanisms for this new catalytic process in PAF's synthesis are discussed in detail.The efficiency and universality of this innovative catalyst system have also been demonstrated in other PAFs'synthesis.This work provides a cheap,facile,and efficient method for scalable synthesis of PAFs and explores their application for high-pressure storage of Xe and Kr.

Application Progress of Porous Materials in Modern Pharmaceutical

Porous materials have regular three-dimensional pore structure, which has unique advantages in the field of modern pharmaceutical. At present, porous materials commonly used in the pharmaceutical field are mainly molecular sieves, macroporous adsorbent resins, activated carbon, etc. In this paper, the application status of these porous materials in the pharmaceutical field is reviewed, and the future development is prospected.

Biomass-derived nitrogen-doped hierarchical porous carbon as efficient sulfur host for lithium–sulfur batteries

Lithium-sulfur(Li-S) battery is a potential energy storage technology with high energy density and low cost. However, the gap between theoretical expectation and practical performance limits its wide implementation. Herein, we report a nitrogen-doped porous carbon derived from biomass pomelo peel as sulfur host material for Li-S batteries. The hierarchical porous architecture and the polar surface introduced by N-doping render a favorable combination of physical and chemical sulfur confinements as well as an expedite electron/ion transfer, thus contributing to a facilitated and stabilized sulfur electrochemistry. As a result, the corresponding sulfur composite electrodes exhibit an ultrahigh initial capacity of 1534.6 mAh g^-1, high coulombic efficiency over 98% upon 300 cycles, and decent rate capability up to 2 C. This work provides an economical and effective strategy for the fabrication of advanced carbonaceous sulfur host material as well as the significant improvement of Li-S battery performance.

Nitrogen-doped hierarchically porous carbon spheres for low concentration CO_(2) capture

Synthesis of spherical carbon beads with effective CO_2 capture capability is highly desirable for large scale application of CO2 sorption, but remains challenging. Herein, a facile and efficient strategy to prepare nitrogen-doped hierarchically porous carbon spheres was developed via co-pyrolyzation of poly(vinylidene chloride) and melamine in alginate gel beads. In this approach, melamine not only serves as the nitrogen precursor, but also acts as a template for the macropores structures. The nitrogen contents in the hierarchically porous carbon spheres reach a high level, ranging from 11.8 wt% to 14.7 wt%, as the melamine amount increases. Owing to the enriched nitrogen functionalities and the special hierarchical porous structure, the carbon spheres exhibit an outstanding CO_2 capture performance, with the dynamic capacity of as much as about 7 wt% and a separation factor about 49 at 25 °C in a gas mixture of CO_2/N_2(0.5:99.5, v/v).

Cocoon Silk-Derived, Hierarchically Porous Carbon as Anode for Highly Robust Potassium-Ion Hybrid Capacitors

Potassium-ion hybrid capacitors(KIHCs) have attracted increasing research interest because of the virtues of potassium-ion batteries and supercapacitors.The development of KIHCs is subject to the investigation of applicable K+storage materials which are able to accommodate the relatively large size and high activity of potassium.Here,we report a cocoon silk chemistry strategy to synthesize a hierarchically porous nitrogen-doped carbon(SHPNC).The as-prepared SHPNC with high surface area and rich N-doping not only offers highly efficient channels for the fast transport of electrons and K ions during cycling,but also provides sufficient void space to relieve volume expansion of electrode and improves its stability.Therefore,KIHCs with SHPNC anode and activated carbon cathode afford high energy of 135 Wh kg-1(calculated based on the total mass of anode and cathode),long lifespan,and ultrafast charge/slow discharge performance.This study defines that the KIHCs show great application prospect in the field of high-performance energy storage devices.

The impact of having an oxygen-rich microporous surface in carbon electrodes for high-power aqueous supercapacitors

The growth of electrical transportation is crucially important to mitigate rising climate change concerns regarding materials supply.Supercapacitors are high-power devices,particularly suitable for public transportation since they can easily store breaking energy due to their high-rate charging ability.Additionally,they can function with two carbon electrodes,which is an advantage due to the abundance of carbon in biomass and other waste materials(i.e.,plastic waste).Newly developed supercapacitive nanocarbons display extremely narrow micropores(<0.8 nm),as it increases drastically the capacitance in aqueous electrolytes.Here,we present a strategy to produce low-cost flexible microporous electrodes with extremely high power density(>100 kW kg^(-1)),using fourty times less activating agent than traditionnal chemically activated carbons.We also demonstrate that the affinity between the carbon and the electrolyte is of paramount importance to maintain rapid ionic diffusion in narrow micropores.Finally,this facile synthesis method shows that low-cost and bio-based free-standing electrode materials with reliable supercapacitive performances can be used in electrochemistry.

High-loading, ultrafine Ni nanoparticles dispersed on porous hollow carbon nanospheres for fast (de)hydrogenation kinetics of MgH_(2)

Magnesium hydride(MgH2) is one of the most promising hydrogen storage materials for practical application due to its favorable reversibility, low cost and environmental benign;however, it suffers from high dehydrogenation temperature and slow sorption kinetics.Exploring proper catalysts with high and sustainable activity is extremely desired for substantially improving the hydrogen storage properties of MgH2. In this work, a composite catalyst with high-loading of ultrafine Ni nanoparticles(NPs) uniformly dispersed on porous hollow carbon nanospheres is developed, which shows superior catalytic activity towards the de-/hydrogenation of MgH2. With an addition of 5wt% of the composite, which contains 90 wt% Ni NPs, the onset and peak dehydrogenation temperatures of MgH2are lowered to 190 and 242 ℃, respectively. 6.2 wt% H2is rapidly released within 30 min at 250 ℃. The amount of H2that the dehydrogenation product can absorb at a low temperature of 150 ℃ in only 250 s is very close to the initial dehydrogenation value. A dehydrogenation capacity of 6.4wt% remains after 50 cycles at a moderate cyclic regime, corresponding to a capacity retention of 94.1%. The Ni NPs are highly active,reacting with MgH2and forming nanosized Mg2Ni/Mg2NiH4. They act as catalysts during hydrogen sorption cycling, and maintain a high dispersibility with the help of the dispersive role of the carbon substrate, leading to sustainably catalytic activity. The present work provides new insight into designing stable and highly active catalysts for promoting the(de)hydrogenation kinetics of MgH2.

A hierarchical porous carbon membrane from polyacrylonitrile/polyvinylpyrrolidone blending membranes: Preparation,characterization and electrochemical capacitive performance

Novel hierarchical porous carbon membranes were fabricated through a simple carbonization procedure of well-defined blending polymer membrane precursors containing the source of carbon polyacrylonitrile （PAN） and an additive of polyvinylpyrrolidone （PVP）, which was prepared using phase inversion method. The as-fabricated materials were further used as the active electrode materials for supercapacitors. The effects of PVP concentration in the casting solution on structure feature and electrochemical capacitive performance of the as-prepared carbon membranes were also studied in detail. As the electrode material for supercapacitor, a high specific capacitance of 278.0 F/g could be attained at a current of 5 mA/cm2 and about 92.90% capacity retention could be maintained after 2000 charge/discharge cycles in 2 mol/L KOH solution with a PVP concentration of 0.3 wt% in the casting solution. The facile hierarchical pore structure preparation method and the good electrochemical capacitive performance make the prepared carbon membrane particularly promising for use in supercapacitor.

Egg shell waste as an activation agent for the manufacture of porous carbon

Egg shell waste was used as an activation agent directly for the manufacture of a biomass-derived porous carbon,which possessed a surface area of 626 m2·g-1 and was rich in nitrogen,sulfur and oxygen functionalities.The activation mechanism was proposed,and the carbon showed its potential to act as an adsorbent for the adsorptive removal of various contaminants from both aqueous and non-aqueous solutions,possessing maximum adsorption capacities of 195.9,185.1,125.5 and 44.6 mg·g-1 for sulfamethoxazole,methyl orange,diclofenac sodium and dibenzothiophene,respectively.Through the utilization of egg shell waste as a sustainable activation agent,this work may help to make the widely applied biomass-derived porous carbons more economical and ecological.

Development of covalent-organic frameworks derived hierarchical porous hollow carbon spheres based LiOH composites for thermochemical heat storage

Under the joint assistance of its excellent storage strength, accessible long storage lifespan, and high heat utilization efficiency, salt hydrate-based thermochemical heat storage(THS) materials give renewable energy an important outlet to alleviate the pressure of underutilization. Herein, an activated hollow spherical carbon(AHSC) with hierarchical porous architectures converted from covalent-organic frameworks(COFs) is constructed and utilized as the supporting matrix for Li OH.THS composite material for the first time. The obtained Li/AHSC_(3) composites have distinguished hydration performance while manifesting impressive storage ability up to 1916.4 k J kg^(-1)with low operating temperature stemming from the collective effect of the void spherical framework, multimodal porosity, and high surface area of AHSC3. And the Li/AHSC3-40 composite with evidently progressed thermal conductivity is capable of realizing 94.5% heat preservation after twenty-five adsorption-desorption cycles, exhibiting its eminent cyclability and great heat transfer performance. This study not only brings new hope for overcoming the underutilization of low-grade heat but also may enlighten new ideas for enriching the application scenarios of COFs-derived carbonaceous materials.