Effect of N-doping-derived solvent adsorption on electrochemical double layer structure and performance of porous carbon

N-doped porous carbon has been extensively investigated for broad electrochemical applications.The performance is significantly impacted by the electrochemical double layer(EDL),which is material dependent and hard to characterize.Limited understanding of doping-derived EDL structure hinders insight into the structure-performance relations and the rational design of high-performance materials.Thus,we analyzed the mass and chemical composition variation of EDL within electrochemical operation by electrochemical quartz crystal microbalance,in-situ X-ray photoelectron spectroscopy,and time-offlight secondary ion mass spectrometry.We found that N-doping triggers specifically adsorbed propylene carbonate solvent in the inner Helmholtz plane(IHP),which prevents ion rearrangement and enhances the migration of cations.However,this specific adsorption accelerated solvent decomposition,rendering rapid performance degradation in practical devices.This work reveals that the surface chemistry of electrodes can cause specific adsorption of solvents and change the EDL structure,which complements the classical EDL theory and provide guidance for practical applications.

Smart Interfacing between Co-Fe Layered Double Hydroxide and Graphitic Carbon Nitride for High-efficiency Electrocatalytic Nitrogen Reduction

Bimetallic compounds such as hydrotalcite-type layered double hydroxides(LDHs)are promising electrocatalysts owing to their unique electronic structures.However,their abilities toward nitrogen adsorption and reduction are undermined since the surface-mantled,electronegative-OH groups hinder the charge transfer between transition metal atoms and nitrogen molecules.Herein,a smart interfacing strategy is proposed to construct a coupled heterointerface between LDH and 2D g-C_(3)N_(4),which is proven by density functional theory(DFT)investigations to be favorable for nitrogen adsorption and ammonia desorption compared with neat LDH surface.The interfaced LDH and g-C_(3)N_(4) is further hybridized with a self-standing TiO_(2) nanofibrous membrane(NM)to maximize the interfacial effect owing to its high porosity and large surface area.Profited from the synergistic superiorities of the three components,the LDH@C_(3)N_(4)@TiO_(2) NM delivers superior ammonia yield(2.07×10^(−9) mol s^(−1) cm^(−2))and Faradaic efficiency(25.3%),making it a high-efficiency,noble-metal-free catalyst system toward electrocatalytic nitrogen reduction.

Predicting dynamics of soil organic carbon mineralization with a double exponential model in different forest belts of China

The dynamics of soil organic carbon （SOC） was analyzed by using laboratory incubation and double exponential model that mineralizable SOC was separated into active carbon pools and slow carbon pools in forest soils derived from Changbai and Qilian Mountain areas. By analyzing and fitting the CO2 evolved rates with SOC mineralization, the results showed that active carbon pools accounted tor 1.0% to 8.5% of SOC with an average of mean resistant times （MRTs） for 24 days, and slow carbon pools accounted for 91% to 99% of SOC with an average of MRTs for 179 years. The sizes and MRTs of slow carbon pools showed that SOC in Qilian Mountain sites was more difficult to decompose than that in Changbai Mountain sites. By analyzing the effects of temperature, soil clay content and elevation on SOC mineralization, results indicated that mineralization of SOC was directly related to temperature and that content of accumulated SOC and size of slow carbon pools from Changbai Mountain and Qilian Mountain sites increased linearly with increasing clay content, respectively, which showed temperature and clay content could make greater effect on mineralization of SOC.

Yolk-shell Si/C composites with multiple Si nanoparticles encapsulated into double carbon shells as lithium-ion battery anodes

The conceptual design of yolk-shell structured Si/C composites is considered to be an effective way to improve the recyclability and conductivity of Si-based anode materials. Herein, a new type of yolk-shell structured Si/C composite (denoted as TSC-PDA-B) has been intelligently designed by rational engineering and precise control. In the novel structure, the multiple Si nanoparticles with small size are successfully encapsulated into the porous carbon shells with double layers benefiting from the strong etching effect of HF. The TSC-PDA-B product prepared is evaluated as anode materials for lithium-ion batteries (LIBs). The TSC-PDA-B product exhibits an excellent lithium storage performance with a high initial capacity of 2108 mAh g^-1 at a current density of 100 mA g^-1 and superior cycling performance of 1113 mAh g^-1 over 200 cycles. The enhancement of lithium storage performance may be attributed to the construction of hybrid structure including small Si nanoparticles, high surface area, and double carbon shells, which can not only increase electrical conductiv让y and intimate electrical contact with Si nanoparticles, but also provide built-in buffer voids for Si nanoparticles to expand freely without damaging the carbon layer. The present findings can provide some scientific insights into the design and the application of advanced Si-based anode materials in energy storage fields.

Investigation on the deactivation cause of lead-zinc double oxide for the synthesis of diphenyl carbonate by transesterification

The deactivation cause of lead-zinc double oxide for synthesis of diphenyl carbonate （DPC） by transesterification of dimethyl carbonate （DMC） with phenol has been investigated. X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, infrared spectroscopy （IR）, thermogravimetry analysis （TG）, atomic absorption spectroscopy and elementary analysis are employed for the catalyst characterization. The results show that, the formation of Pb4O（OC6H5）6 through the reaction of phenol and lead species in the catalyst leads to the crystal phase change of active component and serious leaching of lead, which is the cause of the catalyst deactivation. In addition, the composition of the leached lead is ascertained to be a mixture of Pb4O（OC6H5）6 and PbO with the weight percentage of 62.7% and 37.3%, respectively.

Performance of Electric Double Layer Capacitors using Active Carbons Prepared from Petroleum Coke by KOH and Vapor Re-Etching

The electrochemical storage of energy in a special kind of active carbon materials used as capacitor electrodes is considered. Petroleum coke was used for preparation of carbons with different porosities by KOH and vapor etching with catalysis of FeCI3 in turn. Carbon electrodes were fabricated and used as electrodes of double layer capacitors. Nitrogen adsorption was used to characterize the porous structure of the carbons. The electrochemical performance of the capacitors in 6 mol/L KOH was investigated with constant current charge and discharge experiments. A specific capacitance larger than 160 F/g was achieved with an electrode composed of 75% active carbon with a specific surface area of 1180 m2/g and 20% graphite as conductive agent. Evaluation of capacitor performance was conducted by different techniques, e.g. voltammetry and impedance spectroscopy. Characteristics of the capacitor were also discussed. A hybrid power source consisting of nickel- hydrogen and double layer capacitor was demonstrated by powering successfully a simulated power load encountered in communication equipment.

Carbonation of Sulphoaluminate Cement with Layered Double Hydroxides

The increasing importance of the ecologically minded production of building materials makes it necessary to develop reasonable alternatives to the CO2-intense production of ordinary Portland cement （OPC）. The development of new or modified concrete is an important part of existing strategies to improve performance and minimize life-cycle costs. Therefore, we investigated carbonation resistance properties of sulphoaluminate cement （SAC） concrete incorporating layered double hydroxides （LDHs）. X-ray diffraction （XRD） and IR-spectroscopy were employed to characterize the component and structural changes of LDHs and cement paste before and after carbonation test. Carbonation resistance of concrete was experimentally evaluated. Finally, carbonation of Portland cement and SAC concrete was compared. The experimental results show that carbonation depth decreases remarkably with the addition of LDHs, especially the calcinated LDHs. Carbonation depth of SAC concrete is smaller than that of PC concrete regardless of curing time.

Secondary Activation of Commercial Activated Carbon and its Application in Electric Double Layer Capacitor

The cheap commercial activated carbon (AC) was improved through the secondary activation under steam in the presence of FeCl2 catalyst in the temperature range of 800-950℃ and its application in electric double layer capacitors (EDLCs) with organic electrolyte was studied. The re-activation of AC results in the increases in both specific capacitance and high rate capability of EDLCs. For AC treated under optimized conditions, its discharge specific capacitance increases up to 55.65 F/g, an increase of about 33% as compared to the original AC, and the high rate capability was increased significantly. The good performances of EDLC with improved AC were correlated to the increasing mesoporous ratio.

Effects of Doubled Carbon Dioxide on Rainfall Responses to Large-Scale Forcing:A Two-Dimensional Cloud-Resolving Modeling Study

ABSTRACT Rainfall responses to doubled atmospheric carbon dioxide concentration were investigated through the analysis of two pairs of two-dimensional cloud-resolving model sensitivity experiments. One pair of experiments simulated pre-summer heavy rainfall over southern China around the summer solstice, whereas the other pair of experiments simulated tropical rainfall around the winter solstice. The analysis of the time and model domain mean heat budget revealed that the enhanced local atmospheric warming was associated with doubled carbon dioxide through the weakened infrared radiative cooling during the summer solstice. The weakened mean pre-summer rainfall corresponded to the weakened mean infrared radiative cooling. Doubled carbon dioxide increased the mean tropical atmospheric warming via the enhanced mean latent heat in correspondence with the strengthened mean infrared radiative cooling during the winter solstice. The enhanced mean tropical rainfall was associated with the increased mean latent heat.

Solid base catalysts derived from Ca-M-Al(M = Mg, La, Ce, Y) layered double hydroxides for dimethyl carbonate synthesis by transesterification of methanol with propylene carbonate

Composite solid base catalysts derived from Ca‐M‐Al(M=Mg,La,Ce,Y)layered double hydroxides(LDH)were synthesized,characterized and applied to the transesterification of methanol with propylene carbonate.X‐ray diffraction analyses of the catalysts show that all of the catalysts were in the form of composite oxides.Compared with the Ca‐Al LDH catalyst,the specific surface areas and pore volumes of the catalysts were increased with the introduction of Mg,La or Ce.The catalytic performance of these catalysts increases in the order of Ca‐Y‐Al<Ca‐Al<Ca‐Ce‐Al<Ca‐La‐Al<Ca‐Mg‐Al,which is consistent with the total surface basic amounts of these materials and the formation of especially strong basic sites following modification with Mg and La.The Ca‐Mg‐Al catalyst shows the highest(Ca+Mg):Al atomic ratio,indicating that it likely contains more unsaturated O2?ions,providing it with the highest concentration of very strong basic sites.The recyclability of these catalysts is improved following the addition of Mg,La,Ce or Y,with the Ca‐Mg‐Al maintaining a high level of activity after ten recycling trials.X‐ray diffraction analyses of fresh and used Ca‐Mg‐Al demonstrate that this catalyst is exceptionally stable,which could be of value in practical applications related to heterogeneous catalysis.

Fabrication of cobalt aluminum-layered double hydroxide nanosheets/carbon spheres composite as novel electrode material for supercapacitors

A new design route was presented to fabricate cobalt aluminum-layered double hydroxide(CoAl-LDH)thin layers whichgrow on carbon spheres(CSs)through a growth method.The CoAl-LDH thin layers consist of nanoflakes with a thickness of20nm.The galvanostatic charge-discharge test of the CoAl-LDH/CSs composite shows a great specific capacitance of1198F/g at1A/g(based on the mass of the CoAl-LDH/CSs composite)in6mol/L KOH solution,and the composite displays an impressive specificcapacitance of920F/g even at a high current density of10A/g.Moreover,the composite remains a specific capacitance of928F/gafter1000cycles at2A/g,and the specific capacitance retention is84%,indicating that the composite has high specific capacitance,excellent rate capability and good cycling stability in comparison to pristine CoAl-LDH.

Periodic Motion Planning and Control for Double Rotary Pendulum via Virtual Holonomic Constraints

Periodic motion planning for an under-actuated system is rather difficult due to differential dynamic constraints imposed by passive dynamics, and it becomes more difficult for a system with higher underactuation degree, that is with a higher difference between the number of degrees of freedom and the number of independent control inputs. However, from another point of view, these constraints also mean some relation between state variables and could be used in the motion planning.We consider a double rotary pendulum, which has an underactuation degree 2. A novel periodic motion planning is presented based on an optimization search. A necessary condition for existence of the whole periodic trajectory is given because of the higher underactuation degree of the system. Moreover this condition is given to make virtual holonomic constraint(VHC) based control design feasible. Therefore, an initial guess for the optimization of planning a feasible periodic motion is based on this necessary condition. Then, VHCs are used for the system transformation and transverse linearization is used to design a static state feedback controller with periodic matrix function gain. The controller gain is found through another optimization procedure. The effectiveness of initial guess and performance of the closed-loop system are illustrated through numerical simulations.

Electric Double layer Capacitor Based on Activated Carbon Material

In this study electric double layer capacitors (EDLCs) based on activated carbon material and organic electrolyte (tetraethyl ammonium tetrafluoroborate) were explored. The fabrication method for EDLC is presented and the performance of EDLC was examined by using the cyclic voltammetry, constant current charging and discharging technique, electrochemical impedance spectroscopy measurements. Influence of various components and design parameters on the performance of the capacitors were preliminarily investigated. Up to now, EDLC based on carbon materials can deliver 20.7 W/kg at the discharge rate of I =0.3 mA, together with the energy density of 8.5 Wh/kg. Equivalent series resistance (ESR) is 0.716 Ω·cm 2. The specific power of the capacitor is low and further attempts to raise the power capability of the capacitors are necessary. Some considerations are put forward to further improve the performance of EDLC.

Rational architecture design of yolk/double-shells Si-based anode material with double buffering carbon layers for high performance lithium-ion battery

Among the many strategies to fabricate the silicon/carbon composite,yolk/double-shells structure can be regarded as an effective strategy to overcome the intrinsic defects of Si-based anode materials for Li-ion batteries(LIBs).Hereon,a facile and inexpensive technology to prepare silicon/carbon composite with yolk/double-shells structure is proposed,in which the double buffering carbon shells are fabricated.The silicon/carbon nanoparticles with core-shell structure are encapsulated by SiO_(2)and external carbon layer,and it shows the yolk/double-shells structure via etching the SiO_(2)sacrificial layer.The multiply shells structure not only significantly improves the electrical conductivity of composite,but also effectively prevents the exposure of Si particles from the electrolyte composition.Meanwhile,the yolk/double-shells structure can provide enough space to accommodate the volume change of the electrode during charge/discharge process and avoid the pulverization of Si particles.Moreover,the as-prepared YDS-Si/C shows excellent performance as anode of LIBs,the reversible capacity is as high as 1066 mA h g^(-1) at the current density of 0.5 A g^(-1) after 200 cycles.At the same time,the YDS-Si/C has high capacity retention and good cyclic stability.Therefore,the unique architecture design of yolk/double-shells for Si/C composite provides an instructive exploration for the development of next generation anode materials of LIBs with high electrochemical performances and structural stability.

Characterization of Microporous Activated Carbon Electrodes for Electric Double-layer Capacitors

Activated carbons(ACs) with a wide range of surface areas were made from petroleum coke by means of KOH activation. The electrochemical characterization was carried out for several activated carbons used as polarizable electrodes of electric double-layer capacitors(EDLCs) in an aqueous electrolytic solution. The porous structures and electrochemical double-layer capacitance of the activated carbons were investigated by virtue of nitrogen gas adsorption and constant current cycling(CCC) methods. The relationship among the surface area, pore volume of the activated carbons and specific double-layer capacitance was discussed. It was found that the specific capacitance of ACs increased linearly with the increase of surface area. The presence of mesopores in the activated carbons with very high surface area(>2000 m\+2/g) was not very effective for them to be used as EDLCs. The influence of chemical characteristics of the activated carbons on the double layer formation could be considered to be negligible.

Passively mode-locked 2-μm Tm:YAP laser with a double-wall carbon nanotube absorber

We report on a diode-pumped passively continuous wave （cw） mode-locked Tm：YAP laser with a double-wall carbon nanotube （DWCNT） absorber operating at a wavelength of 2023 nm for the first time, to the best our knowledge. The DWCNT absorber is fabricated on a hydrophilic quartz substrate by using the vertical evaporation technique. The output power is as high as 375 mW. A stable pulse train with a repetition rate of 72.26 MHz is generated with a highest single pulse energy of 5.2 μJ.

Substitution of chemical fertilizer by Chinese milk vetch improves the sustainability of yield and accumulation of soil organic carbon in a double-rice cropping system

The double-rice cropping system is a very important intensive cropping system for food security in China. There have been few studies of the sustainability of yield and accumulation of soil organic carbon (SOC) in the double-rice cropping system following a partial substitution of chemical fertilizer by Chinese milk vetch (Mv). We conducted a 10-year (2008–2017) field experiment in Nan County, South-Central China, to examine the double-rice productivity and SOC accumulation in a paddy soil in response to different fertilization levels and Mv application (22.5 Mg ha^–1). Fertilizer and Mv were applied both individually and in combination (sole chemical fertilizers, Mv plus 100, 80, 60, 40, and 0% of the recommended dose of chemical fertilizers, labeled as F100, MF100, MF80, MF60, MF40, and MF0, respectively). It was found that the grain yields of double-rice crop in treatments receiving Mv were reduced when the dose of chemical fertilizer was reduced, while the change in SOC stock displayed a double peak curve. The MF100 produced the highest double-rice yield and SOC stock, with the value higher by 13.5 and 26.8% than that in the F100. However, the grain yields increased in the MF80 (by 8.4% compared to the F100), while the SOC stock only increased by 8.4%. Analogous to the change of grain yield, the sustainable yield index (SYI) of double rice were improved significantly in the MF100 and MF80 compared to the F100, while there was a slight increase in the MF60 and MF40. After a certain amount of Mv input (22.5 Mg ha^–1), the carbon sequestration rate was affected by the nutrient input due to the stimulation of microbial biomass. Compared with the MF0, the MF100 and MF40 resulted in a dramatically higher carbon sequestration rate (with the value higher by 71.6 and 70.1%), whereas the MF80 induced a lower carbon sequestration rate with the value lower by 70.1% compared to the MF0. Based on the above results we suggested that Mv could partially replace chemical fertilizers (e.g., 40–60%) to improve or maintain the productivity and sustainability of the double-rice cropping system in South-Central China.

Adsorption of K^+ from an aqueous phase onto an activated carbon used as an electric double-layer capacitor electrode

The adsorption capacity and absorption rate for electrolyte onto activated carbon are important parameters used to characterize activated carbon electric double-layer capacitor electrodes. In this paper the pore structure of typical commercial activated carbons, and various Mn-doped activated carbons prepared on a laboratory scale, are described. The pore structure was character-ized by N2 adsorption/desorption isotherms. Isotherms for K+ adsorption onto these activated carbons from the aqueous phase were also obtained. The experimental, equilibrium K+ adsorption data were fitted to the Langmuir, Freundlich or Temkin equations. Adsorption of K+ onto the activated carbons was measured and plotted as a function of time. The adsorption kinetic data were modeled by either pseudo-first or pseudo-second order equations. The Elvoich equation, a liquid film diffusion and an intra-particle diffusion model were used to fit the kinetic data. The results indicate that the adsorption of K+ onto activated carbon is influenced by many factors including pore size distribution, specific surface area and the surface chemistry of the activated carbons. The Temkin equation best describes the equilibrium adsorption data. The pseudo-second order model exactly describes the whole adsorption process, which is controlled by both liquid film and intra-particle diffusion.

Synergistic interaction between redox-active electrolytes and functionalized carbon in increasing the performance of electric double-layer capacitors

The increasing demand of high-performance supercapacitors has aroused great interest in developing specific capacitance and energy density. Active carbon （AC） has attracted much attention as a promising electrode material for electric double-layer capacitors （EDLCs）. Here, a facile strategy has been employed to fabricate high-performance EDLCs using the surface-oxygen functionalized active carbon （FAC） as an electrode and 2 M KOH with K3Fe（CN）6 as an electrolyte. In this system, K3Fe（CN）6 was used as a redox additive to enhance the performance of EDLCs. A 38.5% increase in specific capacitance （207.7 F g-1） was achieved compared with the KOH electrolyte without adding K3Fe（CN）G （152.9 F g-1）, due to the synergistic effects between oxygenic functional groups and redox electrolyte. These findings provide an alternative route to improve the performance of EDLCs, which are promising candidates for the broad applications of high-performance supercapacitors.

Synthesis of Ni/Mg/Al Layered Double Hydroxides and Their Use as Catalyst Precursors in the Preparation of Carbon Nanotubes

Ni/Mg/Al layered double hydroxides(LDHs) with different n(Ni)∶n(Mg)∶n(Al) ratio values were prepared via a coprecipitation reaction. Then Ni/Mg/Al mixed oxides were obtained by calcination of these LDHs precursors. Carbon nanotubes were produced in the catalytic decomposition of propane over the Ni/Mg/Al mixed oxide catalysts. The quality of as-made nanotubes was investigated by SEM and TEM. The nanotubes were multiwall with a high length-diameter ratio and appeared to be flexible. The catalytic activities of these mixed oxides increased with increasing the Ni content. The Ni/Mg/Al mixed oxide with the highest Ni content [n(Ni)/n(Mg)/n(Al)=1/1/1] showed the highest activity and the carbon nanotubes grown on its surface had the best quality.