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.

Reduction of Cr(Ⅵ) with a relative high concentration using different kinds of zero-valent iron powders: Focusing on effect of carbon content and structure on reducibility

Reduction of Cr(VI)using zero-valent iron(ZVI)could not only decrease the amounts of chemicals used for reduction,but also decrease the discharge of sludge.In order to find a desirable ZVI material,reduction of Cr(VI)with a relative high concentration using different kinds of ZVI powders(mainly carbon differences)including reduced Fe,grey cast iron,pig iron,nodular pig iron was carried out.Parameters such as ZVI dosage,type and size affecting on Cr(VI)reduction were firstly examined and grey cast iron was selected as a preferable reducing material,followed by pig iron.Additionally,it was found that the parameters had significant influences on experimental kinetics.Then,morphology and composition of the sample before and after reaction were characterized by SEM,EPMA and XPS analyses to disclose carbon effect on the reducibility.In order to further interpret reaction mechanism,different reaction models were constructed.It was revealed that not only the carbon content could affect the Cr(VI)reduction,but also the carbon structure had an important effect on its reduction.

Electric-Arc Plasma Installation for Preparing Nanodispersed Carbon Structures

An electric-arc plasma installation operated in the hidden anode arrangement is constructed and used for the preparation of carbon nanostructures. A contracted plasma arc generated by a plasma torch using an inert gas is used as heat source. The average mass temperature of arc is higher than 10^4 K, while its power density, which is directly transferred onto the electrode （anode）, is - 2 kW/mm^2. The anode contact area formed on the electrode moves against the arc by way of shifting the electrode and is hidden completely in the interior of plasma gas stream moving towards it. As a result of both the direct plasma attack and the opposite movement of streams in the hidden anode contact area, a temperature higher than 6000 K is reached. Thus, intensive vaporization takes place, which forms a saturated plasma-gas-aerosol phase of the initial material of electrode （anode）. This gas phase is mixed in and carried by the plasma stream. Over that mixed plasma stream, a controlled process of quenching （fixation） is carried out by twisted turbulent fluid streams. After the fixation, the resultant carbon nano-structures are caught by a filter and collected in a bunker.

Effect of temperature and stress on molecular structure and carbon monoxide generation of lignite from Kailuan mining area

In order to analyze the origin of carbon monoxide(CO) in coal seams, stress–strain experiments under temperature of 50, 150 and 250 °C were conducted using lignite from Kailuan mining area. Fourier transform infrared spectroscopy and elemental analysis were carried out before and after deformation of the samples. The results indicated that CO generated at 150 and 250 °C; the gas component was mostly oxygen(O_2), with small amount of carbon dioxide(CO_2), methane(CH_4) and hydrogen(H_2). At 50 °C, O_2 and a little CO_2 were observed and no CO was found. The carbon content of the coal samples increased slightly after deformation, and the oxygen content, H/C ratio, and O/C ratio decreased. The molecular structure of coal displayed different evolution characteristics at various temperatures. At 50 and 150 °C, the falling off of side chains, broken of ether bond and directional realignment of the aliphatic chains resulting in the formation of long chains were the main performance of coal molecular structure evolution. While at 250 °C, the side chains fell off and short chains formed. Furthermore, at both 150 and 250 °C, condensed degree of aromatic ring increased. Under the action of temperature and pressure, CO forms in two ways.The first is that ether bond breaks, oxygen and carbon atoms combine together and forms CO, or O_2 forming in the broken of ether–oxygen bond leads to the oxidation of free radicals and resulting in the formation of CO. And the second is that CO derives from falling off of C=O group.

Microbial community structure and functional metabolic diversity are associated with organic carbon availability in an agricultural soil

Exploration of soil environmental characteristics governing soil microbial community structure and activity may improve our understanding of biogeochemical processes and soil quality. The impact of soil environmental characteristics especially organic carbon availability after 15-yr different organic and inorganic fertilizer inputs on soil bacterial community structure and functional metabolic diversity of soil microbial communities were evaluated in a 15-yr fertilizer experiment in Changping County, Beijing, China. The experiment was a wheat-maize rotation system which was established in 1991 including four different fertilizer treatments. These treatments included： a non-amended control（CK）, a commonly used application rate of inorganic fertilizer treatment（NPK）; a commonly used application rate of inorganic fertilizer with swine manure incorporated treatment（NPKM）, and a commonly used application rate of inorganic fertilizer with maize straw incorporated treatment（NPKS）. Denaturing gradient gel electrophoresis（DGGE） of the 16 S r RNA gene was used to determine the bacterial community structure and single carbon source utilization profiles were determined to characterize the microbial community functional metabolic diversity of different fertilizer treatments using Biolog Eco plates. The results indicated that long-term fertilized treatments significantly increased soil bacterial community structure compared to CK. The use of inorganic fertilizer with organic amendments incorporated for long term（NPKM, NPKS） significantly promoted soil bacterial structure than the application of inorganic fertilizer only（NPK）, and NPKM treatment was the most important driver for increases in the soil microbial community richness（S） and structural diversity（H）. Overall utilization of carbon sources by soil microbial communities（average well color development, AWCD） and microbial substrate utilization diversity and evenness indices（H＇ and E） indicated that long-term inorganic fertilizer with organic amendments incorporated（NPKM, NPKS） could significantly stimulate soil microbial metabolic activity and functional diversity relative to CK, while no differences of them were found between NPKS and NPK treatments. Principal component analysis（PCA） based on carbon source utilization profiles also showed significant separation of soil microbial community under long-term fertilization regimes and NPKM treatment was significantly separated from the other three treatments primarily according to the higher microbial utilization of carbohydrates, carboxylic acids, polymers, phenolic compounds, and amino acid, while higher utilization of amines/amides differed soil microbial community in NPKS treatment from those in the other three treatments. Redundancy analysis（RDA） indicated that soil organic carbon（SOC） availability, especially soil microbial biomass carbon（Cmic） and Cmic/SOC ratio are the key factors of soil environmental characteristics contributing to the increase of both soil microbial community structure and functional metabolic diversity in the long-term fertilization trial. Our results showed that long-term inorganic fertilizer and swine manure application could significantly improve soil bacterial community structure and soil microbial metabolic activity through the increases in SOC availability, which could provide insights into the sustainable management of China＇s soil resource.

Effect of hydrothermal treatment on the carbon structure of Inner Mongolia lignite

Understanding the structural properties of lignite during hydrothermal treatment would aid in predicting the subsequent behavior of coal during the pyrolysis,liquefaction,and gasification processes.Here,hydrothermal treatment of Inner Mongolia lignite(IM)was carried out in a lab autoclave.The distribution of carbon in the lignite was monitored via solid 13C nuclear magnetic resonance spectroscopy,and the functional groups of oxygen in lignite were determined by Fourier transform infrared spectroscopy.The curve-fitting method was used to calculate the content of the functional groups quantitatively.The results show that hydrothermal treatment is an effective method for upgrading the lignite.The side chains of the aromatic ring in lignite are altered,while the main macromolecular structure remains nearly the same.The hydrothermal treatment of IM could be divided into three temperature-dependent stages.The first stage(<493 K)is the decomposition reaction of oxygen functional groups,where the O/C ratio decreases from 0.203 in raw IM to 0.185 for the IM treated at 493 K.In the second stage(493–533 K),hydrolysis of functional groups and hydrogen transfer between water and lignite occur.Here,the ratio of methylene to methyl increases from 0.871 in IM-493 to 1.241 for IM-533,and the content of quinone generates from the condensation of free phenol increased.The third stage(>533 K)involves breakage of the covalent bond,and the content of CH4 and CO in the emission gas clearly increase.

Composition and Microstructure of Magnetron Sputtering Deposited Ti-containing Amorphous Carbon Films

Ti-containing carbon films were deposited by using magnetron sputtering deposition. The composition and microstructure of the carbon films were characterized in detail by combining the techniques of Rutherford backscattering spectrometry （RBS）, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. It is found that carbon films contain Ti 18 at pct; after Ti incorporation, the films consist of titanium carbide; C1s peak appears at 283.4 eV and it could be divided into 283.29 and 284.55 eV, representing sp2 and sp3, respectively, and sp2 is superior to sp3. This Ti-containing film with dominating sp2 bonds is nanocomposites with nanocrystalline TiC clusters embedded in an amorphous carbon matrix, which could be proved by XRD and TEM.

Microwave-assisted Hydrothermal Synthesis of Carbon Materials with Tunable Microstructure

A facile microwave-assisted hydrothermal route has been developed for a synthesis of versatile carbon materials. The monosaccharide fructose aqueous solution was adopted as the starting material, and the p H of the solution was adjusted to be in acidic（pH 4）, neutral（pH 7） and basic（pH 10.5） conditions. The p H buffered fructose solutions were treated at different temperatures by a microwave-assisted hydrothermal technique. As-prepared carbon materials displayed p H and temperature dependent multi-morphologies（porous, spherical or core-shell）, which were determined by transmission and scanning electron microscopic analyses（TEM and SEM）. And the hypothesis of dehydration mechanism of hydrothermal synthesis was analyzed by ultraviolet extinction and Fourier transform infrared spectroscopy. It was found that as compared with normal hydrothermal synthesis, microwave assistance could efficiently increase the production yield and improve the spherical geometry of the carbon particles in neutral condition. By changing the p H of the system, acidic p H induces aggregation of the spheres, while basic p H produces more trends toward core-shell or sponge-like porous structure. The study opens a novel route to the production of polytropic carbon materials and suggests a potential niche market established from the green synthesis.

Influence of Sodium Carbonate Amount on Crystalline Phase and Structure Stability for Doping Nickel Hydroxide

Alpha nickel hydroxide has better performances than commercial beta nickel hydroxide. However, the main defect is that α-phase is difficult to synthesize and easily transformed to β-phase Ni（OH）2 upon aging in a strong alkaline solution. In this study, the Al-Co, Al-Yb, Yb-Co and Al-Yb-Co multiple doping was used respectively. By controlling the amount of sodium carbonate, the α-Ni（OH）2 was prepared by ultrasonic-assisted precipitation. And the influence of sodium carbonate on the crystalline phase and structure stability for alpha nickel hydroxide was studied. The results demonstrate that, with increasing amount, the biphase nickel hydroxide transforms to pure alpha nickel hydroxide gradually, and the structure stability is also improved. When the amount of sodium carbonate is 2 g, the sample still keeps α-Ni（OH）2 after being aged for 30 days, for Al-Yb-Co-Ni（OH）2. And when the amount is less than 2 g, the phase transformations exist in the samples with different extents. These results demonstrated that the amount of sodium carbonate is a critical factor to maintain the structural stability of α-Ni（OH）2.

Data-Driven Design for Targeted Regulation of Heat Transfer in Carbon/Carbon Composite Structure

Targeted regulation of heat transfer in carbon/carbon composite structure is built for cooling electronic device.A three-dimensional data-driven design model coupling genetic algorithm(GA) with self-adaption deep learning for targeted regulation of heat transfer in built structure is proposed.The self-adaption deep learning model predicts the temperature of built structure closer to optimal value in GA model.The distributions of pore and carbon fiber bundles in built structure are optimized by the proposed model.The surface temperature of electronic device in the optimized structures is 19.1%-27.5% lower than that in the initial configurations when the porosity of built structure varies from 3% to 11%.The surface temperature of electronic device increases with an increase in porosity.The built structure with carbon fiber bundles near the surface of electronic device and pore distribution in the middle of structure has a higher heat dissipation capacity compared with that in the initial configuration.Besides,the computation time of the proposed model is less than one tenth compared with that of the traditional genetic algorithm.

Additivity of pore structural parameters of granular activated carbons derived from different coals and their blends

A series of granular activated carbons （GACs） were prepared by briquetting method from Chinese coals of different ranks and their blends, with coal pitch as the binder. Pore structural parameters including BET specific surface area （SBEr）, total pore volume （Vr） and average pore diameter （da） were measured and cal- culated as well as process parameters such as yield of char （CY） and burn-off （B）. The relationship between the pore structural parameters of the GAC from coal blend （BC-GAC） and the ones of the GACs from corresponding single coals （SC-GACs） was analyzed, in which an index, the relative error （δ）, was presented to define the bias between fitted values and experimental values of these parameters of the BC-GACs. The results show that the BC-GAC keeps qualitatively the pore structural features of the SC-GACs; as concerned as the quantitative relationship, the pore structural parameters of the BC-GAC from coal blend consisting of non-caking coals can be obtained by adding proportionally the pore structural parameters of the SC-GACs with a less than 10%. Meanwhile, for the BC-GAC from coal blend containing weak caking bituminous coal, the δ increases up to 25% and the experimental pore size distribution differs greatly from the fitted one.

Modification of CaO-based sorbents prepared from calcium acetate for CO_2 capture at high temperature

CaO-based sorbent is considered to be a promising candidate for capturing CO_2 at high temperature. However,the adsorption capacity of CaO decreases sharply with the increase of the carbonation/calcination cycles. In this study, CaO was derived from calcium acetate(CaAc_2), which was doped with different elements(Mg, Al,Ce, Zr and La) to improve the cyclic stability. The carbonation conversion and cyclic stability of sorbents were tested by thermogravimetric analyzer(TGA). The sorbents were characterized by N_2 isothermal adsorption measurements, scanning electron microscopy(SEM) and X-ray diffraction(XRD). The results showed that the cyclic stabilities of all modified sorbents were improved by doping elements, while the carbonation conversions of sorbents in the 1st cycle were not increased by doping different elements. After 22 cycles, the cyclic stabilities of CaO–Al, CaO–Ce and CaO–La were above 96.2%. After 110 cycles, the cyclic stability of CaO–Al was still as high as 87.1%. Furthermore, the carbonation conversion was closely related to the critical time and specific surface area.

Role of Ni(NO_3)_2 in the preparation of a magnetic coal-based activated carbon

The role of Nil（NO3）2 in the preparation of a magnetic activated carbon is reported in this paper. Magnetic coal-based activated carbons （MCAC） were prepared from Taixi anthracite with low ash content in the presence of Ni（NO3）2. The MCAC materials were characterized by a vibrating sample magnetometer （VSM）, X-ray diffraction （XRD）, a scanning electric microscope （SEM）, and by N2 adsorption. The cylindri- cal precursors and derived char were also subjected to thermogravimetric analysis to compare their behavior of weight losses during carbonization. The results show that MCAC has a larger surface area （1074 m21g） and a higher pore volume （0.5792 cm3/g） with enhanced mesopore ratio （by about 10~）. It also has a high saturation magnetization （1.6749 emu/g） and low coercivity （43.26 Oe）, which allows the material to be magnetically separated. The MCAC is easily magnetized because the nickel salt is con- vetted into Ni during carbonization and activation. Metallic Ni has a strong magnetism on account of electrostatic interaction. Added Ni（NO3）2 catalyzes the carbonization and activation process by accelerat- ing burn off of the carbon, which contributes to the development of mesopores and macropores in the activated carbon.

Optimal activated carbon for separation of CO_2 from(H_2 + CO_2) gas mixture

Seven types of activated carbon were used to investigate the effect of their structure on separation of CO2 from（H2 ＋ CO2） gas mixture by the adsorption method at ambient temperature and higher pressures. The results showed that the limiting factors for separation of CO2 from 53.6 mol% H2 ＋ 46.4 mol% CO2 mixture and from 85.1 mol% H2 ＋ 14.9 mol% CO2 mixture were different at 20 °C and about 2 MPa. The best separation result could be achieved when the pore diameter of the activated carbon ranged from 0.77 to 1.20 nm, and the median particle size was about2.07 lm for 53.6 mol% H2 ＋ 46.4 mol% CO2 mixture and 1.41 lm for 85.1 mol% H2 ＋ 14.9 mol% CO2 mixture. The effect of specific area and pore diameter of activated carbon on separation CO2 from 53.6 mol% H2 ＋ 46.4 mol% CO2 mixture was more significant than that from 85.1 mol% H2 ＋ 14.9 mol% CO2 mixture. CO2 in the gas phase can be decreased from 46.4 mol% to 2.3 mol%–4.3 mol% with a two-stage separation process.

Synthesis, Characterization and Application of A Novel Carbon Bridged Half-metallocene Chromium Catalyst for Methyl Methacrylate Polymerization

A new carbon bridged cyclopentadienyl chromium complex of the type [（C5H4）C（CH3）2 CH2（C5H4N）]CrCl2 was prepared by treatment of CrCl3·（THF）3 in THF solution with the lithium salt of ligand containing cyclopentadienyl and pyridyl groups. The chromium complex was characterized by 1H NMR and elemental analysis（EA）, and the crystal structure was determined by X-ray diffraction analysis. Activated by Al（i-Bu）3, the chromium complex displayed a very high activity for methyl methacrylate（MMA） polymerization. After 24 hours,more than 95.5% MMA was converted to polymethyl methacrylate（PMMA） with a viscosity average molecular weight（Wη） of 416000 g·mol-1 at 60 ℃ for MMA/ Al（i-Bu）3 /chromium catalyst molar ratio of up to 2000：20：1. Effects of temperature, molar ratios of MMA/catalyst and catalyst/cocatalyst on the polymerization have been studied. The high conversion of MMA and high molecular weight of PMMA with narrow molecular weight distribution is caused by the unique stable active site formed by the new chromium complex and aluminum cocatalyst.

Establishment of correlation between reaction kinetics and carbon structures in the char gasification process

For a gasification process,the char-CO_(2)gasification is the controlling step worthwhile to be deeply investigated.The article chosen corn stalk(CS),poplar sawdust(PS)and bagasse residue(BR)as the typical waste species derived from agricultural,forestal and industrial sources.The char-CO_(2)gasification behavior,reaction kinetics and carbon structure were studied to reveal the intrinsic factors determining the reaction kinetics.Generally,the carbon conversion and maximum conversion rate were influenced by the feedstocks species and char preparation temperatures,as influenced by ash proportion,potassium content in ash and carbon structure of char.The char-CO_(2)reaction for CS was subject more to the catalytic effect of alkali compositions,while pore structure affected more the gasification reaction for PS char.The isoconversional kinetic analysis indicated that the gasification reaction became stable at carbon conversion of 0.5.Subsequently,sectionalized kinetic parameters were calculated for the initial gasification temperature to the temperature reaching 50%conversion.The result showed that high initial gasification temperature increased the char-CO_(2)gasification barrier to hardly start the reaction but accelerate the reaction rate.The carbon structure analyses further clarified that the reaction activation energy was highly related to the microcrystalline structure of carbon,while the reaction rate was more determined by carbon pore structure.

Thermal conductivity of carbon nanoring linked graphene sheets:A molecular dynamics investigation

Improving the thermal conduction across graphene sheets is of great importance for their applications in thermal management. In this paper, thermal transport across a hybrid structure lbrmed by two graphene nanoribbons and carbon nanorings （CNRs） was investigated by molecular dynamics simulations. The effects of linker diameter, number, and height on thermal conductivity of the CNRs-graphene hybrid structures were studied respectively, and the CNRs were found effective in transmitting the phonon modes of GNRs. The hybrid structure with 2 linkers showed the highest thermal conductivity of 68.8 W·m^-1·K^-1. Our work presents important insight into fundamental principles governing the thermal conduction across CNR junctions and provides useful guideline for designing CNR-graphene structure with superior thermal conductivity.

Preparation and structural properties of thin carbon films by very-high-frequency magnetron sputtering

Growth and structural properties of thin a-C films prepared by the 60 MHz very-high-frequency（VHF） magnetron sputtering were investigated. The energy and flux of ions impinging the substrate were also analyzed. It is found that the thin a-C films prepared by the 60 MHz sputtering have a lower growth rate, a smooth surface, and more sp3 contents.These features are related to the higher ion energy and the lower ions flux onto the substrate. Therefore, the 60 MHz VHF sputtering is more suitable for the preparation of thin a-C film with more sp3 contents.

One-pot Synthesis of Bio-inspired Layered Materials of 3D Graphene Network/Calcium Carbonate

A bio-inspired layered material of reduced graphene oxide（RGOs） and calcium carbonate was synthesized via a one-pot strategy in DMF/H2O mixed solvent. The experimental results show that the product is a layered material of wrinkled RGOs networks and micron-sized calcium carbonate particles with uniform granular diameter and homogeneous morphology, which are distributed between the layered gallery of the graphene scaffold. The polymorph and the morphology of the in-situ produced calcium carbonate particles can be manipulated by simply changing the temperature scheme. Besides, the graphene oxide was reduced to a certain extent, and the hierarchical wrinkles were generated in the RGOs layer by the in-situ formation of the calcium carbonate particles. This work provides a facile and controllable strategy for synthesizing layered material of RGOs and carbonates, and also presents a platform for making three-dimensional porous wrinkled RGOs networks.

Evolution Mechanism of Carbon Covalent Bond during Coal Activation Using Mixed Atmosphere of H_(2)O and CO_(2)

Adequate destruction of the aromatic structure in coal is key to further reducing the emission of pollutants.In this research,activation reactions of Shenmu coal powder were carried out in a vertical tube furnace.The study investigated the evolution mechanism of carbon covalent bonds during the activation process by altering the ratio of H_(2)O to CO_(2)in the activation atmosphere.The theoretical validation was conducted through density functional calculations.The two gas molecules follow different pathways to increase the reactivity of char.CO_(2)mainly participates in the cross-linking reaction by intensifying branching,while H_(2)O and char have lower adsorption energy barriers and are more likely to generate oxygen-containing functional groups.Gas molecules partially compete for active sites in a mixed gas atmosphere,but there is a synergism between the two effects.The synergism can be attributed to two possibilities.The inclusion of H_(2)O mitigates the generation of five-membered rings to a limited extent,while concurrently enhances the development of oxygen-containing functional groups.Introducing oxygen-containing functional groups can effectively diminish the adsorption energy barrier associated with the interaction between gas molecules and char,consequently leading to a reduction in the energy demand for subsequent bond cleavage.