Proof of Aerobically Autoxidized Self-Charge Concept Based on Single Catechol-Enriched Carbon Cathode Material

The self-charging concept has drawn considerable attention due to its excellent ability to achieve environmental energy harvesting,conversion and storage without an external power supply.However,most self-charging designs assembled by multiple energy harvesting,conversion and storage materials increase the energy transfer loss;the environmental energy supply is generally limited by climate and meteorological conditions,hindering the potential application of these selfpowered devices to be available at all times.Based on aerobic autoxidation of catechol,which is similar to the electrochemical oxidation of the catechol groups on the carbon materials under an electrical charge,we proposed an air-breathing chemical self-charge concept based on the aerobic autoxidation of catechol groups on oxygen-enriched carbon materials to ortho-quinone groups.Energy harvesting,conversion and storage functions could be integrated on a single carbon material to avoid the energy transfer loss among the different materials.Moreover,the assembled Cu/oxygen-enriched carbon battery confirmed the feasibility of the air-oxidation self-charging/electrical discharging mechanism for potential applications.This air-breathing chemical self-charge concept could facilitate the exploration of high-efficiency sustainable air self-charging devices.

Status and Opportunities of Zinc Ion Hybrid Capacitors: Focus on Carbon Materials, Current Collectors, and Separators

Zinc ion hybrid capacitors(ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applications. Carbon-based materials are deemed the competitive candidates for cathodes of ZIHC due to their cost-effectiveness, high electronic conductivity, chemical inertness, controllable surface states, and tunable pore architectures. In recent years, great research efforts have been devoted to further improving the energy density and cycling stability of ZIHCs. Reasonable modification and optimization of carbon-based materials offer a remedy for these challenges. In this review, the structural design, and electrochemical properties of carbon-based cathode materials with different dimensions, as well as the selection of compatible, robust current collectors and separators for ZIHCs are discussed. The challenges and prospects of ZIHCs are showcased to guide the innovative development of carbon-based cathode materials and the development of novel ZIHCs.

Recentadvancesincarbon‐basedmaterials for solar‐driven interfacial photothermal conversion water evaporation:Assemblies,structures,applications,and prospective

The shortage of fresh water in the world has brought upon a serious crisis to human health and economic development.Solar‐driven interfacial photothermal conversion water evaporation including evaporating seawater,lake water,or river water has been recognized as an environmentally friendly process for obtaining clean water in a low‐cost way.However,water transport is restricted by itself by solar energy absorption capacity's limits,especially for finite evaporation rates and insufficient working life.Therefore,it is important to seek photothermal conversion materials that can efficiently absorb solar energy and reasonably design solar‐driven interfacial photothermal conversion water evaporation devices.This paper reviews the research progress of carbon‐based photothermal conversion materials and the mechanism for solar‐driven interfacial photothermal conversion water evaporation,as well as the summary of the design and development of the devices.Based on the research progress and achievements of photothermal conversion materials and devices in the fields of seawater desalination and photothermal electric energy generation in recent years,the challenges and opportunities faced by carbon‐based photothermal conversion materials and devices are discussed.The prospect of the practical application of solar‐driven interfacial photothermal conversion evaporation technology is foreseen,and theoretical guidance is provided for the further development of this technology.

Breaking the temperature limit of hydrothermal carbonization of lignocellulosic biomass by decoupling temperature and pressure

Hydrothermal carbonization(HTC) of lignocellulosic biomass is a promising technology for the production of carbon materials with negative carbon emissions. However, the high reaction temperature and energy consumption have limited the development of HTC technology. In conventional batch reactors, the temperature and pressure are typically coupled at saturated states. In this study, a decoupled temperature and pressure hydrothermal(DTPH) reaction system was developed to decrease the temperature of the HTC reaction of lignocellulosic biomass(rice straw and poplar leaves). The properties of hydrochars were analyzed by scanning electron microscopy(SEM), Fourier transform infrared(FTIR) spectroscopy, X-ray photoelectron spectroscopy(XPS), Raman spectroscopy, X-ray diffraction(XRD), thermogravimetric analyzer(TGA), etc. to propose the reaction mechanism. The results showed that the HTC reaction of lignocellulosic biomass could be realized at a low temperature of 200℃ in the DTPH process, breaking the temperature limit(230℃) in the conventional process. The DTPH method could break the barrier of the crystalline structure of cellulose in the lignocellulosic biomass with high cellulose content, realizing the carbonization of cellulose and hemicellulose with the dehydration, unsaturated bond formation, and aromatization. The produced hydrochar had an appearance of carbon microspheres, with high calorific values, abundant oxygen-containing functional groups, a certain degree of graphitization, and good thermal stability. Cellulose acts not only as a barrier to protect itself and hemicellulose from decomposition, but also as a key precursor for the formation of carbon microspheres. This study shows a promising method for synthesizing carbon materials from lignocellulosic biomass with a carbon-negative effect.

Recent advances in the nanoconfinement of Mg-related hydrogen storage materials:A minor review

Hydrogen is an ideal clean energy because of its high calorific value and abundance of sources.However,storing hydrogen in a compact,inexpensive,and safe manner is the main restriction on the extensive utilization of hydrogen energy.Magnesium(Mg)-based hydrogen storage material is considered a reliable solid hydrogen storage material with the advantages of high hydrogen storage capacity(7.6wt%),good performance,and low cost.However,the high thermodynamic stability and slow kinetics of Mg-based hydrogen storage materials have to be overcome.In this paper,we will review the recent advances in the nanoconfinement of Mg-related hydrogen storage materials by loading Mg particles on different supporting materials,including carbons,metal-organic frameworks,and other materials.Perspectives are also provided for designing high-performance Mg-based materials using nanoconfinement.

The influence of composition of asphaltenes of different genesis on the properties of carbon materials manufactured from them by plasma processing

The results of experimental studies of carbon materials, which are formed in the plasma of a direct current (DC) arc discharge initiated in open air from the asphaltenes of different origins, extracted from the natural asphaltite and from the oil of the Sredne-Ugutskoye Oilfield, are presented. The influence of the initial asphaltene composition on the composition and properties of the resulting carbon materials is analyzed. The initial asphaltenes and the samples of the carbon materials are characterized by the methods of X-ray diffraction, differential thermal analysis, X-ray fluorescence analysis, IR-Fourier spectroscopy, laser diffraction, transmission and scanning electron microscopy. The changes in the composition and structure of the asphaltenes are determined before and after their plasma treatment and the hypotheses are put forward concerning the chemical processes causing the changes in the molecular structure of the samples. As a result of plasma treatment of asphaltenes (100 A, 30 s), it was shown that graphitization occurs, as well as oxidation, and a decrease in sulfur content. Moreover, nanotubes and nano-onions have been detected using electron microscopy. Petroleum asphaltenes after plasma treatment give a less thermostable carbon material, but with a lower content of heteroatoms, and with a large amount of sulfur in the composition of sulfoxide structural fragments. This method is shown to be a promising technology for processing the petroleum feedstock enriched with heavy asphaltene components for the manufacture of carbon nanomaterials: nanotubes, nano-onions and polyhedral graphite.

Spectral and Morphological Analysis of Graphene-Based Two- Dimensional Carbon Materials

This paper describes the spectral and morphological analysis of graphene, N-doped graphene, and graphenemodified with functional groups. The similarities and differences in the surface and microstructure are characterizedby infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, andtransmission electron microscopy. Compared with high-purity graphene, the introduction of functional groups leads to moredefects in the two-dimensional structure. The quality of graphene, reflected by the intensity ratio of peak D and G modesin the Raman spectroscopy, is consistent with that observed by scanning electron microscopy and transmission electronmicroscopy. The infrared spectra of graphene-based two-dimensional carbon materials are different from that of high-puritygraphene, and the absorption peaks of the functional groups are obvious. The X-ray photoelectron spectroscopy resultsillustrate the diverse chemical states of carbon, and the atomic ratio of carbon to oxygen directly reflects the quality ofthe graphene-based materials. The results of electron microscopy and spectroscopic characterization of graphene samplesprovide an excellent basis for a wide range of applications in graphene production and quality control.

Mechanochemical synthesis of oxygenated alkynyl carbon materials with excellent Hg(Ⅱ) adsorption performance from CaC2 and carbonates

Adsorptive removal of heavy metal ions from wastewater is very important,and the key is the development of efficient sorbents.In this work,oxygenated alkynyl carbon materials(OACMs)were synthesized via mechanochemical reaction of CaC_(2) and a carbonate(CaCO_(3),Na2CO_(3),or NaHCO_(3))at ambient temperature.The resultant OACMs are micro mesoporous carbon nanomaterials with high specific area(>648 m2 g^(-1)),highly crosslinked texture,and rich alkynyl and oxygenated groups.The OACMs exhibit excellent Hg(Ⅱ)adsorption due to the soft acid-soft base interaction between alkynyl and Hg(Ⅱ),and OACM-3 derived from CaC_(2) and NaHCO_(3) has the saturated Hg(Ⅱ)adsorbance of 483.9 mg g^(-1)along with good selectivity and recyclability.The adsorption is mainly chemisorption following the Langmuir mode.OACM-3 also shows high adsorbance for other heavy metal ions,e.g.256.6 mg g^(-1)for Pb(II),232.4 mg g^(-1)for Zn(II),and 198.7 mg g^(-1)for Cu(II).This work expands the mechnochemical reaction of CaC_(2)with carbonates and possibly other oxyanionic salts,provides a new synthesis approach for functional alkynyl carbon materials with excellent adsorption performance for heavy metal ions,as well as a feasible approach for CO2 resource utilization.

Enhancing fly ash utilization in backfill materials treated with CO_(2)carbonation under ambient conditions

The environmental concerns resulting from coal-fired power generation that produces large amounts of CO_(2)and fly ash are of great interest.To mitigate,this study aims to develop a novel carbonated CO_(2)-fly ash-based backfill(CFBF)material under ambient conditions.The performance of CFBF was investigated for different fly ash-cement ratios and compared with non-CO_(2)reacted samples.The fresh CFBF slurry conformed to the Herschel-Bulkley model with shear thinning characteristics.After carbonation,the yield stress of the fresh slurry increased significantly by lowering fly ash ratio due to gel formation.The setting times were accelerated,resulting in approximately 40.6%of increased early strength.The final strength decreased when incorporating a lower fly ash ratio(50%and 60%),which was related to the existing heterogeneous pores caused by rapid fluid loss.The strength increased with fly ash content above 70%because additional C-S(A)-H and silica gels were characterized to precipitate on the grain surface,so the binding between particles increased.The C-S(A)-H gel was developed through the pozzolanic reaction,where CaCO_(3)was the prerequisite calcium source obtained in the CO_(2)-fly ash reaction.Furthermore,the maximum CO_(2)uptake efficiency was 1.39 mg-CO_(2)/g-CFBF.The CFBF material is feasible to co-dispose CO_(2)and fly ash in the mine goaf as negative carbon backfill materials,and simultaneously mitigates the strata movement and water lost in post-subsurface mining.

Durability Testing of Composite Aerospace Materials Based on a New Polymer Carbon Fiber-Reinforced Epoxy Resin

In this study,the durability of a new polymer carbonfiber-reinforced epoxy resin used to produce composite material in the aerospacefield is investigated through analysis of the corrosion phenomena occurring at the microscopic scale,and the related infrared spectra and thermal properties.It is found that light and heat can con-tribute to the aging process.In particular,the longitudinal tensile strength displays a non-monotonic trend,i.e.,itfirst increases and then decreases over time.By contrast,the longitudinal compressive and inter-laminar shear strengths do not show significant changes.It is also shown that the inter-laminar shear strength of carbonfiber/epoxy resin composites with inter-laminar hybrid structure is better than that of pure carbonfiber materials.The related resistance to corrosion can be improved by more than 41%.

Carbon-based interface engineering and architecture design for high-performance lithium metal anodes

Metallic lithium(Li)is considered the“Holy Grail”anode material for the nextgeneration of Li batteries with high energy density owing to the extraordinary theoretical specific capacity and the lowest negative electrochemical potential.However,owing to inhomogeneous Li-ion flux,Li anodes undergo uncontrollable Li deposition,leading to limited power output and practical applications.Carbon materials and their composites with controllable structures and properties have received extensive attention to guide the homogeneous growth of Li to achieve high-performance Li anodes.In this review,the correlation between the behavior of Li anode and the properties of carbon materials is proposed.Subsequently,we review emerging strategies for rationally designing high-performance Li anodes with carbon materials,including interface engineering(stabilizing solid electrolyte interphase layer and other functionalized interfacial layer)and architecture design of host carbon(constructing three-dimension structure,preparing hollow structure,introducing lithiophilic sites,optimizing geometric effects,and compositing with Li).Based on the insights,some prospects on critical challenges and possible future research directions in this field are concluded.It is anticipated that further innovative works on the fundamental chemistry and theoretical research of Li anodes are needed.

Boosting Fischer-Tropsch Synthesis via Tuning of N Dopants in TiO_(2)@CN-Supported Ru Catalysts

Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.

Hydrogen generation from NaBH_(4) for portable proton exchange membrane fuel cell

Sodium borohydride(NaBH_(4)) is considered as the most potential hydrogen storage material for portable proton exchange membrane fuel cells(PEMFC)because of its high theoretical hydrogen capacity.However,the slow and poor kinetic stability of hydrogen generation from NaBH_(4) hydrolysis limits its application.There are two main factors influencing the kinetics stability of hydrogen generation from NaBH_(4).One factor is that the alkaline byproducts(NaBO_(2)) of the hydrolysis reaction can increase the pH of the solution,thus inhibiting the reaction process.It mainly happens in the NaBH_(4) solution hydrolysis system.Another factor is that the monotonous increase in reaction temperature leads to uncontrollable and unpredictable hydrolysis rates in the solid NaBH_(4) hydrolysis system.This is due to the excess heat generated from this exothermic reaction in the initial reaction of NaBH_(4) hydrolysis.In this perspective,we summarize the latest research progress in hydrogen generation from NaBH_(4) and emphasize the design principles of catalysts for hydrogen generation from NaBH_(4) solution and solid state NaBH_(4).The importance of carbon as catalyst support material for NaBH_(4) hydrolysis is also highlighted.

Carbon materials for stable Li metal anodes: Challenges, solutions, and outlook

Lithium(Li)metal is regarded as the ultimate anode for next-generation Li-ion batteries due to its highest specific capacity and lowest electrochemical potential.However,the Li metal anode has limitations,including virtually infinite volume change,nonuniform Li deposition,and an unstable electrode-electrolyte interface,which lead to rapid capacity degradation and poor cycling stability,significantly hindering its practical application.To address these issues,intensive efforts have been devoted toward accommodating and guiding Li deposition as well as stabilizing the interface using various carbon materials,which have demonstrated excellent effectiveness,benefiting from their vast variety and excellent tunability of the structure-property relationship.This review is intended as a guide through the fundamental challenges of Li metal anodes to the corresponding solutions utilizing carbon materials.The specific functionalities and mechanisms of carbon materials for stabilizing Li metal anodes in these solutions are discussed in detail.Apart from the stabilization of the Li metal anode in liquid electrolytes,attention has also been paid to the review of anode-free Li metal batteries and solid-state batteries enabled by strategies based on carbon materials.Furthermore,we have reviewed the unresolved challenges and presented our outlook on the implementation of carbon materials for stabilizing Li metal anodes in practical applications.

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.

Carbon materials from melamine sponges for supercapacitors and lithium battery electrode materials: A review

With the increasing energy demand together with the deteriorating environment and decreasing fossil fuel resources,the development of highly efficient energy conversion and storage devices is one of the key challenges of both fundamental and applied research in energy technology.Melamine sponges(MS)with low density,high nitrogen content,and high porosity have been used to design and obtain three‐dimensional porous carbon electrode materials.More importantly,they are inexpensive,environment‐friendly,and easy to synthesize.There have been many reports on the modification of carbonized MS and MS‐based composites for supercapacitor and lithium battery electrode materials.In this paper,recent studies on the fabrication of electrode materials using MS as raw materials have been mainly reviewed,including carbonation,doping activation,and composite modification of MS,and expectations for the development of porous carbon materials for energy storage as a reference with excellent performance,environment‐friendliness,and long life.

Advances in carbon-based thermoelectric materials for high-performance,flexible thermoelectric devices

Waste energy harvesting can contribute to the increase of the efficiency of many industrial processes,which consume energy to produce valuable products.Among all the wasted energy,heat energy is the most abundant,existing in almost any situation.Thermoelectric devices have the capability to harvest and convert the thermal energy into electrical power via the Seebeck effect.With its simple operating principle,thermoelectric devices can be reliable even under the harshest environments,taking advantage of any type of heat source.As a result,various inorganic and organic materials are being explored as thermoelectric materials.Among the reported materials,carbon-based materials are promising in terms of commericialization,due to their nontoxic and abundant nature,and solution processability.In particular,poly(3,4-ethylenedioxythiophene):polystyrene sulfonate(PEDOT:PSS),carbon nanotubes,and graphene are extensively studied as thermoelectric materials owing to their remarkable thermoelectric performance.Also,organic-inorganic hybrid halide perovskites show the potential to be used as future high-performance thermoelectric materials.Here,the progess in carbon materials as thermoelectrics is reviewed in detail,focusing on four base materials(PEDOT:PSS,carbon nanotubes,graphene,and organic-inorganic hybrid halide perovskites).This review illuminates the potential of carbon-based materials in the field of thermoelectrics and their application to next-generation energy devices.

Research progress on carbon materials as negative electrodes in sodium-and potassium-ion batteries

Carbon materials,including graphite,hard carbon,soft carbon,graphene,and carbon nanotubes,are widely used as high-performance negative electrodes for sodium-ion and potassium-ion batteries(SIBs and PIBs).Compared with other materials,carbon materials are abundant,low-cost,and environmentally friendly,and have excellent electrochemical properties,which make them especially suitable for negative electrode materials of SIBs and PIBs.Compared with traditional carbon materials,modifications of the morphology and size of nanomaterials represent effective strategies to improve the quality of electrode materials.Different nanostructures make different contributions toward improving the electrochemical performance of electrode materials,so the synthesis of nanomaterials is promising for controlling the morphology and size of electrode materials.This paper reviews the progress made and challenges in the use of carbon materials as negative electrode materials for SIBs and PIBs in recent years.The differences in Na+and K+storage mechanisms among different types of carbon materials are emphasized.

Multidimensional(0D-3D)functional nanocarbon:Promising material to strengthen the photocatalytic activity of graphitic carbon nitride

As a prospective visible-light-responsive photochemical material,graphitic carbon nitride(g-C_(3)N_(4))has become a burgeoning research hot topics and aroused a wide interest as a metal-free semiconductor in the area of energy utilization and conversion,environmental protection due to its unique properties,such as facile synthesis,high physicochemical stability,excellent electronic band structure,and sustainability.However,the shortcomings of high recombination rate of charge carriers,relatively low electrical conductivity and visible light absorption impede its practical application.Various strategies,such as surface photosensitization,heteroatom deposition,semiconductor hybridization,etc.,have been applied to overcome the barriers.Among all the strategies,functional nanocarbon materials with various dimensions(0D~3D)attract much attention as modifiers of g-C_(3)N_(4)due to their unique electronic properties,optical properties,and easy functionalization.More importantly,the properties of these functional nanocarbon materials can be tuned by various dimensions and thus there will be a way to overcome the defects of g-C_(3)N_(4)by choosing different dimensional carbon materials.Distinguishing from some present reviews,this review starts with the fundamental physicochemical characteristics of g-C_(3)N_(4)materials,followed by analyzing the advantages of functional nanocarbon materials modifying gC_(3)N_(4).Then,we present a systematic introduction to various dimensional carbon materials.The design philosophy of carbon/g-C_(3)N_(4)composites and the advanced studies are exemplified in detail.Finally,a nichetargeting summary and outlook on the major challenges,opportunities for future research in high-powered carbon/g-C_(3)N_(4)composites was proposed.

Promise of commercialization: Carbon materials for low-cost perovskite solar cells

Perovskite solar cells(PVSCs) have attracted extensive studies due to their high power conversion efficiency(PCE)with low-cost in both raw material and processes. However, there remain obstacles that hinder the way to their commercialization. Among many drawbacks in PVSCs, we note the problems brought by the use of noble metal counter electrodes(CEs) such as gold and silver. The costly Au and Ag need high energy-consumption thermal evaporation process which can be made only with expensive evaporation equipment under vacuum. All the factors elevate the threshold of PVSCs' commercialization. Carbon material, on the other hand, is a readily available electrode candidate for the application as CE in the PVSCs. In this review, endeavors on PVSCs with low-cost carbon materials will be comprehensively discussed based on different device structures and carbon compositions. We believe that the PVSCs with carbon-based CE hold the promise of commercialization of this new technology.