Coupling of Adhesion and Anti‑Freezing Properties in Hydrogel Electrolytes for Low‑Temperature Aqueous‑Based Hybrid Capacitors

Solid-state zinc-ion capacitors are emerging as promising candidates for large-scale energy storage owing to improved safety,mechanical and thermal stability and easy-to-direct stacking.Hydrogel electrolytes are appealing solid-state electrolytes because of eco-friendliness,high conductivity and intrinsic flexibility.However,the electrolyte/electrode interfacial contact and anti-freezing properties of current hydrogel electrolytes are still challenging for practical applications of zinc-ion capacitors.Here,we report a class of hydrogel electrolytes that couple high interfacial adhesion and anti-freezing performance.The synergy of tough hydrogel matrix and chemical anchorage enables a well-adhered interface between hydrogel electrolyte and electrode.Meanwhile,the cooperative solvation of ZnCl2 and LiCl hybrid salts renders the hydrogel electrolyte high ionic conductivity and mechanical elasticity simultaneously at low temperatures.More significantly,the Zn||carbon nanotubes hybrid capacitor based on this hydrogel electrolyte exhibits low-temperature capacitive performance,delivering high-energy density of 39 Wh kg^(-1)at-60°C with capacity retention of 98.7%over 10,000 cycles.With the benefits of the well-adhered electrolyte/electrode interface and the anti-freezing hydrogel electrolyte,the Zn/Li hybrid capacitor is able to accommodate dynamic deformations and function well under 1000 tension cycles even at-60°C.This work provides a powerful strategy for enabling stable operation of low-temperature zinc-ion capacitors.

Lignin‐derived carbon with pyridine N‐B doping and a nanosandwich structure for high and stable lithium storage

Biomass‐derived carbon is a promising electrode material in energy storage devices.However,how to improve its low capacity and stability,and slow diffusion kinetics during lithium storage remains a challenge.In this research,we propose a“self‐assembly‐template”method to prepare B,N codoped porous carbon(BN‐C)with a nanosandwich structure and abundant pyridinic N‐B species.The nanosandwich structure can increase powder density and cycle stability by constructing a stable solid electrolyte interphase film,shortening the Li^(+) diffusion pathway,and accommodating volume expansion during repeated charging/discharging.The abundant pyridinic N‐B species can simultaneously promote the adsorption/desorption of Li^(+)/PF_(6)^(−) and reduce the diffusion barrier.The BN‐C electrode showed a high lithium‐ion storage capacity of above 1140 mAh g^(−1) at 0.05 A g^(−1) and superior stability(96.5% retained after 2000 cycles).Moreover,owing to the synergistic effect of the nanosandwich structure and pyridinic N‐B species,the assembled symmetrical BN‐C//BN‐C full cell shows a high energy density of 234.7Wh kg^(−1),high power density of 39.38 kW kg−1,and excellent cycling stability,superior to most of the other cells reported in the literature.As the density functional theory simulation demonstrated,pyridinic N‐B shows enhanced adsorption activity for Li^(+) and PF_(6)^(−),which promotes an increase in the capacity of the anode and cathode,respectively.Meanwhile,the relatively lower diffusion barrier of pyridinic N‐B promotes Li^(+) migration,resulting in good rate performance.Therefore,this study provides a new approach for the synergistic modulation of a nanostructure and an active site simultaneously to fabricate the carbon electrode material in energy storage devices.

Structure design and electrochemical properties of carbon-based single atom catalysts in energy catalysis:A review

Single atom catalysts(SACs) possessing regulated electronic structure, high atom utilization, and superior catalytic efficiency have been studied in almost all fields in recent years. Carbon-based supporting SACs are becoming popular materials because of their low cost, high electron conductivity, and controllable surface property. At the stage of catalysts preparation, the rational design of active sites is necessary for the substantial improvement of activity of catalysts. To date, the reported design strategies are mainly about synthesis mechanism and synthetic method. The level of understanding of design strategies of carbon-based single atom catalysts is requiring deep to be paved. The design strategies about manufacturing defects and coordination modulation of catalysts are presented. The design strategies are easy to carry out in the process of drawing up preparation routes. The components of carbon-based SACs can be divided into two parts: active site and carbon skeleton. In this review, the manufacture of defects and coordination modulation of two parts are introduced, respectively. The structure features and design strategies from the active sites and carbon skeletons to the overall catalysts are deeply discussed.Then, the structural design of different nano-carbon SACs is introduced systematically. The characterization of active site and carbon skeleton and the detailed mechanism of reaction process are summarized and analyzed. Next, the applications in the field of electrocatalysis for oxygen conversion and hydrogen conversion are illustrated. The relationships between the superior performance and the structure of active sites or carbon skeletons are discussed. Finally, the conclusion of this review and prospects on the abundant space for further promotion in broader fields are depicted. This review highlights the design and preparation thoughts from the parts to the whole. The detailed and systematic discussion will provide useful guidance for design of SACs for readers.

Advances in selective conversion of carbohydrates into 5-hydroxymethylfurfural

Converting carbohydrates into 5-hydroxymethylfurfural(5-HMF) is an attractive and promising route for value-added utilization of agricultural and forestry biomass resource. As an important platform compound, 5-HMF possesses high active furan structure with hydroxymethyl and aldehyde group for production of various bio-chemicals and materials, meanwhile, which suffer from low stability and poor yield during the industrial biorefinery process. Hence, selective production of 5-HMF with high-yield and low-cost has attracted extensive attention from scientific and industrial researchers. This review sorted and described the latest advanced research on solvent and catalyst system, as well as energy field effect for production of 5-HMF with different feedstock in detail, emphatically discussing the solvent effect and its synergistic effect with other aspects. Besides, the future prospects and challenges for production of 5-HMF from carbohydrates were also presented, which provide a profound insight into industrial 5-HMF process with economic and environmental feature.

For more and purer hydrogen-the progress and challenges in water gas shift reaction

The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to ammonia synthesis and other reactions. Advanced catalysts have been developed for both high and low-temperature reactions and are widely used in industry. In recent years, supported metal nanoparticle catalysts have been researched due to their high metal utilization. Low-temperature catalysts have shown promising results, including high selectivity, high shift rates, and higher activity potential. Additionally, significant progress has been made in removing trace CO through the redox reaction in electrolytic cell. This paper reviews the development of WGS reaction catalysts, including the reaction mechanism, catalyst design, and innovative research methods. The catalyst plays a crucial role in the WGS reaction, and this paper provides an instant of catalyst design under different conditions. The progress of catalysts is closely related to the development of advanced characterization techniques.Furthermore, modifying the catalyst surface to enhance activity and significantly increase reaction kinetics is a current research direction. This review goals to stimulate a better understanding of catalyst design, performance optimization, and driving mechanisms, leading to further progress in this field.

Porous heterostructure of graphene/hexagonal boron nitride as an efficient electrocatalyst for hydrogen peroxide generation

Compared with the traditional heteroatom doping,employing heterostructure is a new modulating approach for carbon-based electrocatalysts.Herein,a facile ball milling-assisted route is proposed to synthesize porous carbon materials composed of abundant graphene/hexagonal boron nitride(G/h-BN)heterostructures.Metal Ni powder and nanoscale h-BN sheets are used as a catalytic substrate/hard template and“nucleation seed”for the formation of the heterostructure,respectively.As-prepared G/h-BN heterostructures exhibit enhanced electrocatalytic activity toward H_(2)O_(2) generation with 86%-95%selectivity at the range of 0.45-0.75 V versus reversible hydrogen electrode(RHE)and a positive onset potential of 0.79 versus RHE(defined at a ring current density of 0.3 mA cm^(-2))in the alkaline solution.In a flow cell,G/h-BN heterostructured electrocatalyst has a H_(2)O_(2) production rate of up to 762 mmol g_(catalyst)^(-1) h^(-1) and Faradaic efficiency of over 75%during 12 h testing,superior to the reported carbon-based electrocatalysts.The density functional theory simulation suggests that the B atoms at the interface of the G/h-BN heterostructure are the key active sites.This research provides a new route to activate carbon catalysts toward highly active and selective O_(2)-to-H_(2)O_(2) conversion.

Co_(2)N Nanoparticles Anchored on N-Doped Active Carbon as Catalyst for Oxygen Reduction Reaction in Zinc–Air Battery

The development of efficient catalytic electrode toward oxygen reduction reaction(ORR)is still a great challenge for the wide use of zinc–air batteries.Herein,Co_(2)N nanoparticles(NPs)anchored on N-doped carbon from cattail were verified with excellent catalytic performances for ORR.The onset and half-wave potentials over the optimal catalyst reach to 0.96 V and 0.84 V,respectively.Current retention rates of 96.8%after 22-h test and 98.8%after running 1600 s were obtained in 1 M methanol solution.Density functional theory simulation proposes an apparently increased electronic states of Co_(2)N in N-doped carbon layer close to the Fermi level.Higher charge density,favorable adsorption,and charge transfer of intermediates originate from the coexistence of Co_(2)N NPs and N atoms in carbon skeleton.The superior catalytic activity of composites also was confirmed in zinc–air batteries.This novel catalytic property and controllable preparation approach of Co_(2)Ncarbon composites provide a promising avenue to fabricate metal-containing catalytically active carbon from biomass.

Metallurgical pyrolysis toward Co@Nitrogen-doped carbon composite for lithium storage

Elemental state matter-heteroatom-doped carbon composites are of great importance for the development of anode in lithium ion batteries(LIBs).In this article,metal–organic frameworks(MOFs)are adopted as precursor to prepare Co composites via metallurgical pyrolysis under controllable conditions.The obtained nitrogen-doped porous carbon-Co nanocomposite possesses core–shell structure(Co@C–N).Co@C–N exhibits the best Li storage performances as anode active matter.After the 200th cycles at current density of 0.2 A g^(-1),a reversible capacity of 870 mAh g^(-1)is retained.A reversible capacity of 275 mAh g^(-1)still maintains with 5 A g^(-1).Co@C–N presents a high reversible capacity with excellent cycle stability.Considering the corresponding experimental and theoretical results,the Co0-based N-doped porous carbon composite is proposed to work as LIBs anode matter.These results provide a new design idea for electrode matters of metallic ion battery,and demonstrate that MOFs pyrolysis is an effective method for the construction of elemental state anode materials.

An improved theoretical procedure for the pore-size analysis of activated carbon by gas adsorption

Amorphous carbon materials play a vital role in adsorbed natural gas(ANG) storage. One of the key issues in the more prevalent use of ANG is the limited adsorption capacity, which is primarily determined by the porosity and surface characteristics of porous materials. To identify suitable adsorbents, we need a reliable computational tool for pore characterization and, subsequently, quantitative prediction of the adsorption behavior. Within the framework of adsorption integral equation(AIE), the pore-size distribution(PSD) is sensitive to the adopted theoretical models and numerical algorithms through isotherm fitting. In recent years, the classical density functional theory(DFT) has emerged as a common choice to describe adsorption isotherms for AIE kernel construction. However,rarely considered is the accuracy of the mean-field approximation(MFA) commonly used in commercial software. In this work, we calibrate four versions of DFT methods with grand canonical Monte Carlo(GCMC) molecular simulation for the adsorption of CH_4 and CO_2 gas in slit pores at 298 K with the pore width varying from 0.65 to 5.00 nm and pressure from 0.2 to 2.0 MPa. It is found that a weighted-density approximation proposed by Yu(WDA-Yu) is more accurate than MFA and other non-local DFT methods. In combination with the trapezoid discretization of AIE, the WDA-Yu method provides a faithful representation of experimental data, with the accuracy and stability improved by 90.0% and 91.2%, respectively, in comparison with the corresponding results from MFA for fitting CO_2 isotherms. In particular, those distributions in the feature pore width range(FPWR)are proved more representative for the pore-size analysis. The new theoretical procedure for pore characterization has also been tested with the methane adsorption capacity in seven activated carbon samples.

Kinetics and Mechanism of the Uncatalyzed Esterification of Acid-Rich Oil with Glycerol

In this paper, non-catalytic high temperature deacidification process of glycerol rich in acid oil was studied. Through orthogonal experiment, the primary and secondary order of influencing factors was temperature, glycerol dosage and reaction time, and the optimal process conditions were further verified: The ratio of fatty acid to glycerol is 1:1.2, the reaction temperature is 240°C, and the acid value can be reduced to 1.66 mg KOH/g for 2 h. In addition, the activation energy of the reaction was 54.93 kJ/mol by kinetic study. Combined with the K1 value of each reaction, it was confirmed that the temperature rise was conducive to the progress of the reaction. Finally, the high temperature ionization theory of glycerol is put forward, and the mechanism of auto-catalyzed deacidification reaction of glycerol is deduced by using this theory. This theory not only explains this study, but also perfectly explains the slow reaction time of low glycerol dosage.

Oxygen vacancy promoting artificial atom(RuPd)by d-orbital coupling for efficient water dissociation

Rational design of highly active catalysts for breaking hydrogen-oxygen bonds is of great significance in energy chemical reactions involving water.Herein,an efficient strategy for the artificial atom(RuPd)established by d-orbital coupling and adjusted by oxygen vacancy(V_(O))is verified for water dissociation.As an experimental verification,the turnover frequency of RuPd-TiO_(2)-VO(RuPdTVO)catalyst in ammonia borane hydrolysis reaches up to 2750 min^(−1)(26,190 min−1 based on metal dispersion)in the absence of alkali,exceeding the highest active catalysts(Rh-based catalysts).The d-orbital coupling effect between Ru and Pd simulates the outer electronic structure of Rh.Electron transfer from V_(O) to(RuPd)constructs an electron-rich state of active sites that further enhances the ability of the artificial atom to dissociate water.This work provides an effective electronic regulation strategy from V_(O) and artificial atom constructed by d-orbital coupling effect for efficient water dissociation.

A process insight into production of ethyl levulinate via a stepwise fractionation

Ethyl levulinate(EL)is a key biomass-derived compounds due to its socio-economic benefits for the synthesis of commodity chemicals.Herein,we proposed an efficient one-step bamboo conversion to EL in ethanol,and a novel stepwise fractionation to purify EL and lignocellulose degradation products.A proton acid,due to its high catalytic efficiency,yielded 26.65%EL in 120 min at 200℃.The productions of ethyl glucoside and 5-ethoxymethylfurfural were analyzed in terms of by-products formation.To the best of our knowledge,there is no single report on catalyst for one step synthesis of EL directly from bamboo,as well as a stepwise fractionation to purify EL.Due to similar physiochemical properties in each fraction,the platform molecules could broaden a new paradigm of bamboo biomass utilization for renewable energy and value-added biochemicals.In addition,glucose,ethyl glucoside,corn starch,and microcrystalline cellulose were also investigated as substrates,so that the reaction intermediates of this one-pot procedure were identified and a possible reaction mechanism was proposed.

Fabricating pyridinic N-B sites in porous carbon as efficient metal-free electrocatalyst in conversion CO_(2)into CH_(4)

Electrochemical reduction of CO_(2)(CO_(2)RR)to value-added chemicals is an attractive strategy for greenhouse gas mitigation and carbon recycle.Carbon material is one of most promising electrocatalysts but its product selectivity is limited by few modulating approaches for active sites.Herein,the predominant pyridinic N-B sites(accounting for 80%to all N species)are fabricated in hierarchically porous structure of graphene nanoribbons/amorphous carbon.The graphene nanoribbons and porous structure can accelerate electron and ion/gas transport during CO_(2)RR,respectively.This carbon electrocatalyst exhibits excellent selectivity toward CO_(2)reduction to CH_(4)with the faradaic efficiency of 68%at−0.50 V vs.RHE.As demonstrated by density functional theory,a proper adsorbed energy of∗CO and∗CH_(2)O are generated on the pyridinic N-B site resulting into high CH_(4)selectivity.Therefore,this study provides a novel method to modulate active sites of carbon-based electrocatalyst to obtain high CH_(4)selectivity.

Improving bifunctional catalytic activity of biochar via in-situ growth of nickel-iron hydroxide as cathodic catalyst for zinc-air batteries

Expanding the application scenarios of wood-derived biochar guided by the conversion of traditional energy to new energy shows great promise as a field.As thrilling energy conversion apparatus,zinc-air batteries(ZABs)require cathode catalysts with high oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)activities and stability.Herein,two-dimensional nickel-iron hydroxide nanosheets were creatively assembled in N-doped wood-derived biochar(NiFe-LDH@NC)by an in-situ growth method.The categorized porous organization in wood-derived biochar facilitates the rapid seepage of electrolytes and rapid diffusion of reaction gases.The unique interfacial structure of biochar and NiFe-LDH accelerates electron transfer during oxygen electrocatalysis,and endows NiFe-LDH@NC with first-class catalytic activity and durability for ORR and OER.The ZAB derived from NiFe-LDH@NC showed elevated discharge productivity and cycle endurance,making it promising for viable applications.This work provided a convenient way for the conversion of wood-derived biochar to high-value added electrocatalysts.

Advances and challenges of cellulose functional materials in sensors

As the most abundant natural polymer material on the earth,cellulose is a promising sustainable sensing material due to its high mechanical strength,excellent biocompatibility,good degrada-tion,and regeneration ability.Considering the inherent advantages of cellulose and the success of modern sensors,applying cellulose to sensors has always been the subject of considerable investigation,and significant progress has been made in recent decades.Herein,we reviewed the research progress of cellulose functional materials(CFMs)in recent years.According to the different sources of cellulose,the classification and preparation methods for the design and func-tionalization of cellulose were summarized with the emphasis on the relationship between their structure and properties.Besides,the applications of advanced sensors based on CFMs in recent years were also discussed.Finally,the potential challenges and prospects of the development of sensor based on CFMs were outlined.

Investigation on the mechanism of structural reconstruction of biochars derived from lignin and cellulose during graphitization under high temperature

The structural reconstruction mechanism of lignin and cellulose-derived biochars during direct graphitization under ultra-high temperatures was intensively investigated.It was demonstrated that cellulose-derived char was almost composed of carbon microcrystallites,whereas lignin-derived char reserved some of its skeleton structures,and such structural difference played a vital role in the morphology of formed graphitic layers.The results illustrated that the graphitized lignin-derived sample under 2800℃had graphitic degree of 89.53%,interlayer spacing of 0.3363 nm and electronic conductivity of 104.6 S cm^(−1),while cellulose-derived sample had graphitic degree of 76.74%,layer distance of 0.3374 nm,and electronic conductivity of only 48.8 S cm^(−1).Combined with the results of structural analysis of the chars derived from lignin and cellulose,it was inferred that the stable and aromatic ring containing skeleton structure in lignin was beneficial to the ring-enlarging reconstruction and the formation of large areas of continuous graphitic layers during graphitizing process,leading to high electronic conductivity.Meanwhile,the interwoven microcrystallites in cellulose-derived char strongly restricted the expanding of continuous lamellar graphitic areas even at such ultra-high temperature,causing the formation of turbostratic structure with numerous structural defects as well,and finally resulting in relatively lower electronic conductivity.This work is expected to provide theoretical guidance for preparing high-performance functional carbon materials from lignocellulosic biomass.

Establishment of green graphite industry:Graphite from biomass and its various applications

Resource-and energy-efficient biomass exploitation for green graphite production is one of the most effective strategies for satisfying graphite demand while minimizing energy consumption and carbon emissions.This study investigated green graphite production from biomass waste and its applications to establish a green graphite industry.Biomass pyrolysis and catalytic graphitization of biochar were studied first to produce green graphite.The optimized green graphite exhibited a reversible capacity of 264 mA h/g and 97%capacity retention over 100 cycles in a half-cell.Green graphite electrodes with a resistivity lower than 5μΩm were fabricated by using organic fraction bio-oil as a green binder.Other green graphite applications,including printing,conductive printing,pencils,and refractories,were also achieved.The overall process of graphite anode and electrode synthesis from biomass waste and short-rotation energy crops was modeled.Approx.95 kg of battery graphite or 109 kg of metallurgical graphite electrodes can be produced per ton of biomass with low primary energy consumption and carbon footprint.Prominently,the modeling result and life cycle assessment demonstrated that,for the production of battery graphite from biomass waste,net-negative-CO_(2)emissions(−0.57 kg CO_(2)-eq/kg graphite powders)with net-negative-primary energy consumption(−28.31 MJ/kg graphite powders)was achieved.

Wood-derived integrated air electrode with Co-N sites for rechargeable zinc-air batteries

The sluggish reaction kinetics in oxygen reduction reaction(ORR)is one of the bottlenecks in next generation energy conversion systems.The integrated design strategy based on simultaneously constructing active sites and forming porous carbon network will address this concern by facilitating charge exchange,mass transfer and electron transportation.In this article,a three-dimensional integrated air electrode(Co-N@ACS)containing Co-N sites and hierarchically porous carbon is fabricated via growth of Co-doped ZIF-8 in activated wood substrate and synchronous pyrolysis.The optimized integrated air electrodes exhibit ultrahigh ORR activity(E_(1/2)=0.86 V).Co-N sites provide outstanding ORR activity,and hierarchically porous structures facilitate oxygen diffusion and electrolyte penetration.Aqueous zinc-air battery assembled with Co-N@ACS possesses open-circuit voltage of 1.46 V,peak power density of 155 mW cm^(-2) and long-term stability of 540 cycles(180 h).Solid-state zinc-air battery assembled with Co-N@ACS shows open-circuit voltage up to 1.36 V and low charge-discharge voltage gap(0.8 V).This design strategy paves the way for the conversion of wood biomass to integrated air electrodes and catalytically active carbon for next generation energy storage and conversion devices.

The modulating effect of N coordination on single-atom catalysts researched by Pt-N_(x)-C model through both experimental study and DFT simulation

N-doped carbon-based single-atom catalysts(NC-SACs) are widely researched in various electrochemical reactions due to high metal atom utilization and catalytic activity.The catalytic activity of NC-SACs originates from the coordinating structure between single metal site(M) and the doped nitrogen(N) in carbon matrix by forming M-N_(x)-C structure(1≤x≤4).The M-N4-C structure is widely considered to be the most stable and effective catalytic site.However,there is no in-depth research for the "x" modulation in Pt-Nx-C structure and the corresponding catalytic properties.Herein,atomically dispersed Pt on N-doped carbon(Pt-NC) with Pt-Nx-C structure(1≤x≤4),as a research model,is fabricated by a ZIF-8 template and applied to catalytic oxygen reduction.Different carbonization temperatures are used to control N loss,and then modulate the N coordination of Pt-Nx-C structure.The Pt-NC has the predictable low half-wave potential(E_(1/2)) of 0.72 V vs RHE compared to the Pt/C 20% of 0.81 V due to low Pt content.Remarkably,the Pt-NC shows a high onset potential(1.10 V vs RHE,determined for j=-0.1 mA cm^(2)) and a high current density of 5.2 mA cm^(-2),more positive and higher than that of Pt/C 20%(0.96 V) and 4.9 mA cm^(-2),respectively.As the structural characterization and DFT simulation confirmed,the reducing PtN coordination number induces low valence of Pt atoms and low free energy of oxygen reduction,which is responsible for the improved catalytic activity.Furthermore,the Pt-NC shows high mass activity(172 times higher than that of Pt/C 20%),better stability and methanol crossover resistance.

Liquefaction of bamboo biomass and production of three fractions containing aromatic compounds

Depolymerization of lignin to produce value-added aromatic monomers has attracted increasing attention since these monomers can be used as phenol replacement in production of phenolic resins.Here a one-pot depolymerization of bamboo lignin was investigated to obtain aromatic platforms with low molecular weight using acidic catalyst and ethanol.Three fractions(1#,2#,and 3#)containing different molecular weight distributions of aromatic compounds could be efficiently extracted using water-organic solvent system via a stepwise fractionation process by gradual removal of solvent.The fractions distribution was found to be primarily dependent on the reaction temperature and time.When the temperature was increased from 160°C to 200°C,the yield of fractions containing aromatic products increased significantly from 19.1 wt%to 27 wt%,the same change trend was found by changing the time,and the yield of aromatic products increased from 22.4%to 26.7%with an increase of time from 10 min to 30 min.The bioproducts were characterized by using gas chromatography/mass spectrometry(GC-MS),gel permeation chromatography(GPC)and two-dimensional heteronuclear single-quantum coherence(2D HSQC NMR).As evidenced by GC-MS spectra,the three fractions were mainly comprised of phenolic derivatives,and the relative contents of phenolic compounds took up about 80%of the total area of each fraction.With the similar physiochemical properties of the fractions,aromatic platforms could provide a new paradigm of bamboo lignin utilization for renewable energy and value-added biochemicals.