As a substitute for synthetic ammonia under mild condition, electrocatalytic nitrogen reduction reaction(NRR) provides a hopeful approach for the development of ammonia. Nevertheless, the current development of NRR el...As a substitute for synthetic ammonia under mild condition, electrocatalytic nitrogen reduction reaction(NRR) provides a hopeful approach for the development of ammonia. Nevertheless, the current development of NRR electrocatalysts is far from enough and a systematic research is needed to gain a better improvement. This article presents that 2 D C_(3)N_(4)-NV with a large specific surface area and abundant nitrogen vacancies is prepared by a simple and feasible method, and used as a metal-free catalyst for electrocatalytic NRR. Experiment result and density functional theory(DFT) calculation reveal that nitrogen vacancies in 2 D C_(3)N_(4)-NV can act as an efficient active site for catalytic NRR, which is conducive to capturing and activating N_(2), lowering Gibbs free energy(DG) in reaction and inhibiting hydrogen evolution reaction(HER) at the same time. In addition, the larger specific surface area also makes more active site exposed, which is good for the contact between the electrolyte and the active site, thus enhancing its NRR activity. The electrocatalyst shows an excellent catalytic activity for NRR in 0.1 M HCl, including Faradaic efficiency of 10.96%, NH_(3) yields of 17.85 lg h^(-1) mg_(cat)^(-1)., and good stability(over 20 h).展开更多
In this paper, three kinds of MgO with different specific surface area were prepared, and their effects on the catalytic performance of nickel catalysts for the carbon dioxide reforming of methane were investigated. T...In this paper, three kinds of MgO with different specific surface area were prepared, and their effects on the catalytic performance of nickel catalysts for the carbon dioxide reforming of methane were investigated. The results showed that MgO support with the higher specific surface area led to the higher dispersion of the active metal, which resulted in the higher initial activity. On the other hand, the specific surface area of MgO materials might not be the dominant factor for the basicity of support to chemisorb and activate CO2, which was another important factor for the performance of catalysts. Herein, Ni/MgO(CA) catalyst with proper specific surface area and strong ability to activate CO2exhibited stable catalytic property and the carbon species deposited on the Ni/MgO(CA) catalyst after 10 h of reaction at 650 ?C were mainly activated carbon species.展开更多
The relationship between the specific surface area(SSA) of rust and the electrochemical behavior of rusted steel under wet-dry acid corrosion conditions was investigated. The results showed that the corrosion curren...The relationship between the specific surface area(SSA) of rust and the electrochemical behavior of rusted steel under wet-dry acid corrosion conditions was investigated. The results showed that the corrosion current density first increased and then decreased with increasing SSA of the rust during the corrosion process. The structure of the rust changed from single-layer to double-layer, and the γ-FeOOH content decreased in the inner layer of the rust with increasing corrosion time; by contrast, the γ-FeOOH content in the outer layer was constant. When the SSA of the rust was lower than the critical SSA corresponding to the relative humidity during the drying period, condensed water in the micropores of the rust could evaporate, which prompted the diffusion of O_2 into the rust and the following formation process of γ-FeOOH, leading to an increase of corrosion current density with increasing corrosion time. However, when the SSA of the rust reached or exceeded the critical SSA, condensate water in the micro-pores of the inner layer of the rust could not evaporate which inhibited the diffusion of O_2 and decreased the γ-FeOOH content in the inner rust, leading to a decrease of corrosion current density with increasing corrosion time.展开更多
Effects of specific surface area and tiny amount of impurities of reactive alumina on the workability, sinte- ring and high temperature mechanical strength of corun- dum based castables were investigated. The results ...Effects of specific surface area and tiny amount of impurities of reactive alumina on the workability, sinte- ring and high temperature mechanical strength of corun- dum based castables were investigated. The results show that the presence of reactive alumina with high specific surface area leads to accelerating of the hydration of calcium aluminate cement, thus shortening the working time and setting time of the castables, which can be as- cribed that the critical energy barrier for stable nuclei of hydration products of cement can be reduced by the high specific surface area of reactive alumina. The sintering of the corundum based castables can be accelerated by the reactive alumina with high specific surface area and high amount of impurities, however, the reactive alumina with too high specific surface area and impurities can al- so lead to noticeable shrinkage of castables. In addition, high temperature mechanical strength of corundum based castables can be decreased by the higher amount of trace impurities of reactive alumina due to formation of low- melting phase at high temperatures.展开更多
More than 500 datasets from the literature have been used to evaluate the relationships of specific surface area (SSA),cation exchange capacity (CEC) and activity versus the liquid limit (LL).The correlations gave R^2...More than 500 datasets from the literature have been used to evaluate the relationships of specific surface area (SSA),cation exchange capacity (CEC) and activity versus the liquid limit (LL).The correlations gave R^2 values ranging between 0.71 and 0.92.Independent data were also used to validate the correlations.Estimated SSA values slightly overestimate the measured SSA up to 100 m^2/g.Regarding the estimated CEC values,they overestimated the measured CEC values up to 20 meq/(100 g).A probabilistic approach was performed for the correlations of SSA,CEC and activity versus LL.The analysis shows that the relations of SSA,CEC and activity with LL are robust.Using the LL values,it is possible to assess other basic engineering properties of clays.展开更多
Carbon deposition on nickel powders in methane involves three stages in different reaction temperature ranges. Temperature programing oxidation test and Raman spectrum results indicated the formation of complex and or...Carbon deposition on nickel powders in methane involves three stages in different reaction temperature ranges. Temperature programing oxidation test and Raman spectrum results indicated the formation of complex and ordered carbon structures at high deposition temperatures. The values of I(D)/I(G) of the deposited carbon reached 1.86, 1.30, and 1.22 in the first, second, and third stages, respectively. The structure of carbon in the second stage was similar to that in the third stage. Carbon deposited in the first stage rarely contained homogeneous pyrolytic deposit layers. A kinetic model was developed to analyze the carbon deposition behavior in the first stage. The rate-determining step of the first stage is supposed to be interfacial reaction. Based on the investigation of carbon deposition kinetics on nickel powders from different resources, carbon deposition rate is suggested to have a linear relation with the square of specific surface area of nickel particles.展开更多
Developing efficient oxygen evolution reaction(OER) electrocatalysts such as transition metal sulfides(TMSs) is of great importance to advance renewable hydrogen fuel toward further practical applications.Herein,NiCoS...Developing efficient oxygen evolution reaction(OER) electrocatalysts such as transition metal sulfides(TMSs) is of great importance to advance renewable hydrogen fuel toward further practical applications.Herein,NiCoS_(2) nanoparticles well decorated on double-sided N-doped reduced graphene oxide sheets(NiCoS_(2)/rGO) are prepared from an Al-containing ternary NiCoAl-layered double hydroxide precursor(NiCoAl-LDH) grown on GO support as an OER electrocatalyst.The Al-confinementassisted sulfurization,followed by selective acid treatment,endows the resulting NiCoS_(2)/rGO composite with the advantages:well-dispersed NiCoS_(2) nanoparticles,dualsided rGO support,as well as a large specific surface area of 119.4 m^(2)·g^(-1) and meso-/macroporous size distribution.The NiCoS_(2)/rGO electrocatalyst exhibits an overpotential of 273 mV at 10 mA·cm^(-2) and a good stability of 24 h,which outperform those of the counterparts of NiS_(2)/rGO and CoS_(2)/rGO.The results of electrochemical active surface area and electrochemical impedance spectra experimentally provide convincing rationales of the information of active sites and good conductivity,both underpin the enhanced electrocatalytic performances.展开更多
Adding fumed silica(Si0_(2))has been considered as an effective method for tailoring the phase morphology and performance of elastomer-toughened plastic binary blends.It has been demonstrated that the selective distri...Adding fumed silica(Si0_(2))has been considered as an effective method for tailoring the phase morphology and performance of elastomer-toughened plastic binary blends.It has been demonstrated that the selective distribution of SiO_(2) plays a decisive role in the mechanical properties of plastic/elastomer/SiO_(2)nanocomposites,especially for the impact toughness.In this work,we aim to illuminate the role of specific surface area in controlling their selective distribution of fumed SiO_(2) and consequent mechanical properties of plastic/elastomer binary blends.Three types of SiO_(2) with different specific surface areas were incorporated into polylactide/ethylene-co-vinyl-acetate(PLA/EVA)model blends by melt blending directly.It was found that the selective distribution of SiO_(2) is largely determined by their specific surface areas,i.e.SiO_(2) nanoparticles with low specific surface area has a stronger tendency to be located at the interface between PLA matrix and EVA dispersed phase as compared to those with high specific surface area.The specific surface area-dependent interfacial selective distribution of SiO_(2) is mainly attributed to the extent of increased viscosity of EVA dispersed phase in which SiO_(2)nanoparticles are initially dispersed and resultant migration rate of SiO_(2) nanoparticles.The interfacial localized SiO_(2) nanoparticles induce an obvious enhancement in the impact toughness with strength and modulus well maintained.More importantly,in the case of the same interfacial distribution,toughening efficiency is increased with the specific surface area of SiO_(2).Therefore,this is an optimum specific surface area of SiO_(2) for the toughening.This work not only provides a novel way to manipulate the selective distribution of SiO_(2) in elastomer-toughened plastic blends toward high-performance,but also gives a deep insight into the role of interfacial localized nanoparticles in the toughening mechanism.展开更多
In this work,a facile"carbonization-activation"strategy is developed to synthesize N,P-codoped hierarchical porous carbon.Phosphoric acid is innovatively introduced during the hydrothermal process to achieve...In this work,a facile"carbonization-activation"strategy is developed to synthesize N,P-codoped hierarchical porous carbon.Phosphoric acid is innovatively introduced during the hydrothermal process to achieve in-situ P doping as well as create abundant pores,and the employment of sodamide is of vital importance to simultaneously serve as activating agent and N-source to succeed a high-level N doping.Thus,the obtained samples exhibit a unique three-dimensional hierarchical structure with an ultra-high specific surface area(3646 m^(2)g^(-1))and ultra-high N-doping level(9.81 at.%).Computational analyses confirm that N,P co-doping and higher N content can enhance active sites and widen potential differences of carbon materials to improve their capacitance.The as-prepared carbon materials demonstrate superior electrochemical performances,such as an ultra-high capacitance of 586 Fg^(-1)at 1 Ag^(-1),a superior rate capability of 409 Fg^(-1)at 20 Ag^(-1),and excellent long-term stability of 97%capacitance retention after10,000 cycles in 6 M KOH.Moreover,an assembled symmetric supercapacitor delivers a high energy density of 28.1 Wh kg^(-1)at the power density of 450 W kg^(-1)in 1 M Na_(2)SO_(4),demonstrating a great potential for applications in supercapacitors.展开更多
An improved biosorbent of thiourea modified chitosan microsphere(TMCM) with high specific surface,favorable mechanical strength and excellent adsorption performance had been synthesized via microfluidic technology. ...An improved biosorbent of thiourea modified chitosan microsphere(TMCM) with high specific surface,favorable mechanical strength and excellent adsorption performance had been synthesized via microfluidic technology. Polyethylene glycol was used as a significant component added in aqueous solution of chitosan to produce such microspheres through droplets forming, chemical crosslinking and pores creating. For the improvement of adsorption capacity, thiourea was considered as an excellent choice in increasing amino functional group by graft modification. The SEM, FTIR and EDS were employed to detect distinct features of TMCM. Copper(Ⅱ) was used to test the adsorption performance of TMCM. The experimental results indicated that TMCM exhibited higher adsorption capacity(q_e= 60.6 mg g_(-1)) and faster adsorption rate than that non-modified chitosan microsphere(NMCM).The adsorption kinetic was described well by the pseudo-second order kinetic model, which suggested that chemical adsorption along with electrons transferring was dominant in adsorption process.展开更多
Biochar produced from pyrolysis of biomass has been developed as a platform carbonaceous material that can be used in various applications.The specific surface area(SSA)and functionalities such as N-containing functio...Biochar produced from pyrolysis of biomass has been developed as a platform carbonaceous material that can be used in various applications.The specific surface area(SSA)and functionalities such as N-containing functional groups of biochar are the most significant properties determining the application performance of biochar as a carbon material in various areas,such as removal of pollutants,adsorption of CO_(2)and H2,catalysis,and energy storage.Producing biochar with preferable SSA and N functional groups is among the frontiers to engineer biochar materials.This study attempted to build machine learning models to predict and optimize specific surface area of biochar(SSA-char),N content of biochar(N-char),and yield of biochar(Yield-char)individually or simultaneously,by using elemental,proximate,and biochemical compositions of biomass and pyrolysis conditions as input variables.The predictions of Yield-char,N-char,and SSA-char were compared by using random forest(RF)and gradient boosting regression(GBR)models.GBR outperformed RF for most predictions.When input parameters included elemental and proximate compositions as well as pyrolysis conditions,the test R^(2) values for the single-target and multi-target GBR models were 0.90-0.95 except for the two-target prediction of Yield-char and SSA-char which had a test R^(2) of 0.84 and the three-target prediction model which had a test R^(2) of 0.81.As indicated by the Pearson correlation coefficient between variables and the feature importance of these GBR models,the top influencing factors toward predicting three targets were specified as follows:pyrolysis temperature,residence time,and fixed carbon for Yield-char;N and ash for N-char;ash and pyrolysis temperature for SSA-char.The effects of these parameters on three targets were different,but the trade-offs of these three were balanced during multi-target ML prediction and optimization.The optimum solutions were then experimentally verified,which opens a new way for designing smart biochar with target properties and oriented application potential.展开更多
A facile synthesis procedure is proposed to prepare homogeneous Zr and Ti co-doped SBA-15(Zr-Ti-SBA-15)with high specific surface area of 876.0m2 g−1.Based on“masking mechanism”from tanning,lactic acid was used as m...A facile synthesis procedure is proposed to prepare homogeneous Zr and Ti co-doped SBA-15(Zr-Ti-SBA-15)with high specific surface area of 876.0m2 g−1.Based on“masking mechanism”from tanning,lactic acid was used as masking agent to obtain the uniform distribution of Zr and Ti species in the SBA-15 framework.The obtained materials were characterized by powder X-ray diffraction(XRD),nitrogen adsorption-desorption isotherms,scanning electron microscope(SEM),transmission electron microscope(TEM)and X-ray photoelectron(XPS).The results reveal that in mesoporous materials,the presence of lactic acid gives rise to the uniform distribution of Zr and Ti species.The adsorption equilibrium and kinetic studies of Zr-Ti-SBA-15 materials show that the adsorption process conforms to the Langmuir isotherm and pseudo-second-order kinetic model,respectively.Regenerational experiments show that the Zr-Ti-SBA-15 displays a significant adsorption ability for methylene blue(MB)(up to 291.6 mg/g),along with good reusability,indicating promising potentials of commercialization.Methodologically,this work provides a wide range of possibilities for further development of SBA-15 based on bimetallic and sewage disposal.展开更多
A series of alumina samples were prepared using β-cyclodextrin as the non-surfactant template. These samples were characterized by XRD, BET and TEM. The results showed that the alumina samples prepared using β-cyclo...A series of alumina samples were prepared using β-cyclodextrin as the non-surfactant template. These samples were characterized by XRD, BET and TEM. The results showed that the alumina samples prepared using β-cyclodextrin template had the higher surface areas (124-484 m^2/g), larger pore volumes (0.7-1.27 mL/g) and more thermal stability than samples prepared without using β-cyclodextrin.展开更多
Potassium-ion hybrid capacitors(PIHCs)are widely regarded as highly promising energy storage devi-ces,due to their exceptional energy density,impressive power density,and abundant potassium resources.Unfor-tunately,re...Potassium-ion hybrid capacitors(PIHCs)are widely regarded as highly promising energy storage devi-ces,due to their exceptional energy density,impressive power density,and abundant potassium resources.Unfor-tunately,restricted by the inherent capacitive storage mechanism,the carbon cathodes possess a much lower specific capacity than battery-type anodes.Therefore,designing high-performance carbon cathodes is extremely urgent for the development of PIHCs.Herein,N,O co-doped porous carbon(NOPC)was fabricated through the NaCl hard template method and combined KOH/melamine chemical activation technique,displaying the characteris-tics of abundant N/O content(4.7 at%/16.9 at%),ultrahigh specific surface area(3092 m^(2)g^(-1))and hierarchical pore network.The designed NOPC cathode delivers a high specific capacity(164.4 mAh.g^(-1)at 0.05 A.g^(-1))and superior cyclability(95.1%retention ratio at 2 A·g^(-1)over 2500 cycles).Notably,the adjustable ratio of micropores to mesopores facilitates the achievement of the optimal bal-ance between capacity and rate capability.Moreover,the pseudocapacitance can be further augmented through the incorporation of N/O functional groups.As expected,the graphitel/NOPC based PIHC possesses_a high energy density of 113 Wh.kg-at 747 W.kg^(-1)and excellent capacity retention of 84.4%fter 400 cycles at 1.0 A·g^(-1).This work introduces a novel strategy for designing carbon cathodes that enhances the electrochemical performance of PIHCs.展开更多
[Objectives]This study was conducted to explore the differences in physicochemical properties and surface properties of biochar from different sources.[Methods]Four kinds of materials including rice husk and corn stra...[Objectives]This study was conducted to explore the differences in physicochemical properties and surface properties of biochar from different sources.[Methods]Four kinds of materials including rice husk and corn straw were prepared at 450℃by the limited-oxygen program temperature control method into biochar,and the differences in physicochemical properties and surface properties of the biochar from different sources were studied.[Results]All four kinds of biochar were alkaline(pH=8.7-10.0).Corn straw biochar had the highest organic carbon content(653.6 g/kg),while rice husk biochar had the lowest organic carbon content(486.1 g/kg).Corn straw biochar had the highest nitrogen content(2.7%),while rice husk biochar had the lowest nitrogen content(0.75%).Corn straw biochar had the highest total phosphorus content(5.64 g/kg),while rice husk biochar had the lowest total phosphorus content(1.1 g/kg).Rice straw biochar had the highest total potassium content(53.1 g/kg),while rice husk biochar had the lowest total potassium content(10.6 g/kg).The four types of biochar were all porous,but their pore structure sizes and shapes were different to certain degrees.The order of the specific surface areas of the four types of biochar was rice stalk biochar>corn stalk biochar>wheat stalk biochar>rice husk biochar;the order of the pore volumes was rice stalk biochar>corn stalk biochar>wheat stalk biochar Charcoal>rice husk biochar;and the pore sizes ranked as wheat stalk biochar>corn stalk biochar>rice husk biochar>rice stalk biochar.The biochar from different sources ranked according to the comprehensive evaluation of all indicators as corn straw biochar>wheat straw biochar>rice straw biochar>rice husk biochar.[Conclusions]This study provides reference data for the preparation process of biochar from industrial and agricultural wastes and its application and promotion.展开更多
To meet the emission standard of nitrogen oxides(NOx)in the flue gas of batch furnaces through dry adsorption,a calcium-silica inorganic adsorbent was prepared with limestone and quartz as raw materials.Sample Cu-BTC ...To meet the emission standard of nitrogen oxides(NOx)in the flue gas of batch furnaces through dry adsorption,a calcium-silica inorganic adsorbent was prepared with limestone and quartz as raw materials.Sample Cu-BTC 1#was obtained by solvothermal synthesis,drying and purification in vacuum at 120℃using trimesic acid(H3BTC)and copper nitrate trihydrate(Cu(NO_(3))2·3H_(2)O)as raw materials;likewise,sample Cu-BTC 3#was obtained at 200℃.Sample Cu-BTC 2#was obtained by hydrothermal synthesis,drying and purification in air(metal-organic frameworks,1,3,5-benzene tricarboxylic acid copper).The two types of materials were tested in terms of the NO_(2) adsorption,and then the specific surface area,pore volume,NO_(2) adsorption performance,phase composition,microstructure and thermal stability of the adsorbent materials were exploredvia N_(2) physical adsorption-desorption,SEM,XRD and TG characterization.The results show that:(1)the Cu-BTC samples have higher adsorption capacity than the calcium-silica adsorbent,in which sample Cu-BTC 3#has the largest specific surface area and pore volume,thus adsorption capacity for NO_(2);(2)the calcium-silica adsorbent has better thermal stability and lower total mass loss during the entire process than the Cu-BTC samples;sample Cu-BTC 2#has the best thermal stability among the three Cu-BTC samples,and the metal Cu active sites of the Cu-BTC samples can be exposed at least above 150℃.展开更多
Aqueous sols and gels of tungstic acid were prepared from Na2WO4 with protonated cation-exchange resin. Nano-tungsten oxide of a microporous lamella was synthesized by means of washing of WO3· 2H2O with distilled...Aqueous sols and gels of tungstic acid were prepared from Na2WO4 with protonated cation-exchange resin. Nano-tungsten oxide of a microporous lamella was synthesized by means of washing of WO3· 2H2O with distilled water under ultrasonic wave agitation and centrifuging repeatedly, and the specific surface area tended to increase gradually with washing and centrifuging. The sample of centrifuged 7 h has more than 2 times highs specific surface area and more high photocatalytic activity . The mechanisms are also discussed.展开更多
Silica aerogels were prepared at ambient drying by using ethanol/trimethylchlorosilane (TMCS)/heptane solution as pore water exchange and surface modification of the wet gel before drying. The obtained silica aeroge...Silica aerogels were prepared at ambient drying by using ethanol/trimethylchlorosilane (TMCS)/heptane solution as pore water exchange and surface modification of the wet gel before drying. The obtained silica aerogels exhibit a sponge-like structure with uniform pore size distribution. The effects of heat-treatment on the hydrophobicity, specific surface area and other properties were investigated. The results indicated that the hydrophobicity of silica aerogels could be maintained up to 350℃. With increasing heating temperature, hydrophobicity decreased, and became completely hydrophilic after heat-treatment at 500℃. Brunaueremmitt-teller (BET) surface area results indicated that the specific surface area of silica aerogels increased with increasing heating temperature in the range of 150-500℃. The effects of heat-treatment on the morphology and chemical bonding state of silica aerogels were investigated by scanning electron microscopy (SEM), differential temperature analysis (DTA) and Fourier-transform infrared spectroscopy (FT-IR).展开更多
Kozeny-Carman(KC) equation is a well-known relation between hydraulic conductivity and pore properties in porous material. The applications of KC equation to predicting saturated hydraulic conductivities of sands and ...Kozeny-Carman(KC) equation is a well-known relation between hydraulic conductivity and pore properties in porous material. The applications of KC equation to predicting saturated hydraulic conductivities of sands and non-expansive soils are well documented. However, KC equation is incapable of predicting saturated hydraulic conductivity of expansive soil(e.g. bentonite) well. Based on a new dualpore system, this study modified KC equation for improving the prediction of saturated hydraulic conductivities of bentonites. In this study, an assumption that inter-layer space(micropore) has limited effect on fluid flow performance of compacted bentonite was adopted. The critical parameters including total porosity and total tortuosity in conventional KC equation were replaced by macroporosity and tortuosity of macropore, respectively. Macroporosity and microporosity were calculated by basal spacing of compacted bentonite, which was estimated by assuming that specific surface area is changeable during saturation process. A comprehensive comparison of bentonite’s saturated hydraulic conductivity predictions, including modified KC equation proposed in this study, conventional KC equation, and prediction method based on diffuse double layer(DDL) theory, was carried out. It was found that the predicted saturated hydraulic conductivity of bentonites calculated using modified KC equation fitted the experimental data better than others to a certain extent.展开更多
Large surface area,high conductivity,and rich active site of carbon electrode materials are necessary characteristics for energy storage devices.However,high conductivity and high nitrogen doping of carbon electrode m...Large surface area,high conductivity,and rich active site of carbon electrode materials are necessary characteristics for energy storage devices.However,high conductivity and high nitrogen doping of carbon electrode materials are difficult to coordinate.Here,a facile method via the carbonization of nitrogen-containing Schiff base polymer has been developed to prepare high conductivity and high nitrogen-doped hierarchical porous carbon.The organic components with a benzene ring structure in the polymer promote the formation of more sp^(2)-graphitized carbon,which is beneficial for the improvement of electrical conductivity.Nitrogen-doped hierarchical porous carbon calcined at 900℃ under the NH3 atmosphere possesses high nitrogen content of 7.48 at%,a large specific surface area of 1613.2m2/g,and high electrical conductivity of 2.7 S/cm.As electrode materials in an aqueous-based supercapacitor,nitrogen-doped hierarchical porous carbon exhibits superior specific capacitance of 385 F/g at 1 A/g as well as excellent rate performance(242 and 215 F/g at a current density of 100 and 200 A/g,respectively).In addition,the specific capacitance of electrode measured in a two-electrode system is 335 F/g at 1 A/g,and the long-term cycling stability can be achieved with more than 94%initial capacitance after 10000 cycles.The constructed symmetric supercapacitor delivers high energy density and high power density.The outstanding electrochemical performances combined with the novel and scalable synthetic approach make the nitrogen‐doped hierarchical porous carbon potential electrode material for electrochemical devices.展开更多
基金funded by the National Natural Science Foundation of China (21802058 and 21872066)the Fundamental Research Funds for the Central Universities (China, lzujbky-2020-42)the Natural Science Foundation of Gansu Province (20JR5RA225)。
文摘As a substitute for synthetic ammonia under mild condition, electrocatalytic nitrogen reduction reaction(NRR) provides a hopeful approach for the development of ammonia. Nevertheless, the current development of NRR electrocatalysts is far from enough and a systematic research is needed to gain a better improvement. This article presents that 2 D C_(3)N_(4)-NV with a large specific surface area and abundant nitrogen vacancies is prepared by a simple and feasible method, and used as a metal-free catalyst for electrocatalytic NRR. Experiment result and density functional theory(DFT) calculation reveal that nitrogen vacancies in 2 D C_(3)N_(4)-NV can act as an efficient active site for catalytic NRR, which is conducive to capturing and activating N_(2), lowering Gibbs free energy(DG) in reaction and inhibiting hydrogen evolution reaction(HER) at the same time. In addition, the larger specific surface area also makes more active site exposed, which is good for the contact between the electrolyte and the active site, thus enhancing its NRR activity. The electrocatalyst shows an excellent catalytic activity for NRR in 0.1 M HCl, including Faradaic efficiency of 10.96%, NH_(3) yields of 17.85 lg h^(-1) mg_(cat)^(-1)., and good stability(over 20 h).
基金supported by the South-Central University for Nationalities(CZZ12002)
文摘In this paper, three kinds of MgO with different specific surface area were prepared, and their effects on the catalytic performance of nickel catalysts for the carbon dioxide reforming of methane were investigated. The results showed that MgO support with the higher specific surface area led to the higher dispersion of the active metal, which resulted in the higher initial activity. On the other hand, the specific surface area of MgO materials might not be the dominant factor for the basicity of support to chemisorb and activate CO2, which was another important factor for the performance of catalysts. Herein, Ni/MgO(CA) catalyst with proper specific surface area and strong ability to activate CO2exhibited stable catalytic property and the carbon species deposited on the Ni/MgO(CA) catalyst after 10 h of reaction at 650 ?C were mainly activated carbon species.
基金the National Natural Science Foundation of China(Project No.51571027)for funding support
文摘The relationship between the specific surface area(SSA) of rust and the electrochemical behavior of rusted steel under wet-dry acid corrosion conditions was investigated. The results showed that the corrosion current density first increased and then decreased with increasing SSA of the rust during the corrosion process. The structure of the rust changed from single-layer to double-layer, and the γ-FeOOH content decreased in the inner layer of the rust with increasing corrosion time; by contrast, the γ-FeOOH content in the outer layer was constant. When the SSA of the rust was lower than the critical SSA corresponding to the relative humidity during the drying period, condensed water in the micropores of the rust could evaporate, which prompted the diffusion of O_2 into the rust and the following formation process of γ-FeOOH, leading to an increase of corrosion current density with increasing corrosion time. However, when the SSA of the rust reached or exceeded the critical SSA, condensate water in the micro-pores of the inner layer of the rust could not evaporate which inhibited the diffusion of O_2 and decreased the γ-FeOOH content in the inner rust, leading to a decrease of corrosion current density with increasing corrosion time.
文摘Effects of specific surface area and tiny amount of impurities of reactive alumina on the workability, sinte- ring and high temperature mechanical strength of corun- dum based castables were investigated. The results show that the presence of reactive alumina with high specific surface area leads to accelerating of the hydration of calcium aluminate cement, thus shortening the working time and setting time of the castables, which can be as- cribed that the critical energy barrier for stable nuclei of hydration products of cement can be reduced by the high specific surface area of reactive alumina. The sintering of the corundum based castables can be accelerated by the reactive alumina with high specific surface area and high amount of impurities, however, the reactive alumina with too high specific surface area and impurities can al- so lead to noticeable shrinkage of castables. In addition, high temperature mechanical strength of corundum based castables can be decreased by the higher amount of trace impurities of reactive alumina due to formation of low- melting phase at high temperatures.
文摘More than 500 datasets from the literature have been used to evaluate the relationships of specific surface area (SSA),cation exchange capacity (CEC) and activity versus the liquid limit (LL).The correlations gave R^2 values ranging between 0.71 and 0.92.Independent data were also used to validate the correlations.Estimated SSA values slightly overestimate the measured SSA up to 100 m^2/g.Regarding the estimated CEC values,they overestimated the measured CEC values up to 20 meq/(100 g).A probabilistic approach was performed for the correlations of SSA,CEC and activity versus LL.The analysis shows that the relations of SSA,CEC and activity with LL are robust.Using the LL values,it is possible to assess other basic engineering properties of clays.
基金financially supported by the National Program on Key Basic Research Project of China (973 Program, No. 2012CB215405)the National Natural Science Foundation of China (No. 51174022)
文摘Carbon deposition on nickel powders in methane involves three stages in different reaction temperature ranges. Temperature programing oxidation test and Raman spectrum results indicated the formation of complex and ordered carbon structures at high deposition temperatures. The values of I(D)/I(G) of the deposited carbon reached 1.86, 1.30, and 1.22 in the first, second, and third stages, respectively. The structure of carbon in the second stage was similar to that in the third stage. Carbon deposited in the first stage rarely contained homogeneous pyrolytic deposit layers. A kinetic model was developed to analyze the carbon deposition behavior in the first stage. The rate-determining step of the first stage is supposed to be interfacial reaction. Based on the investigation of carbon deposition kinetics on nickel powders from different resources, carbon deposition rate is suggested to have a linear relation with the square of specific surface area of nickel particles.
基金financially supported by the National Natural Science Foundation of China(No.U1607128)。
文摘Developing efficient oxygen evolution reaction(OER) electrocatalysts such as transition metal sulfides(TMSs) is of great importance to advance renewable hydrogen fuel toward further practical applications.Herein,NiCoS_(2) nanoparticles well decorated on double-sided N-doped reduced graphene oxide sheets(NiCoS_(2)/rGO) are prepared from an Al-containing ternary NiCoAl-layered double hydroxide precursor(NiCoAl-LDH) grown on GO support as an OER electrocatalyst.The Al-confinementassisted sulfurization,followed by selective acid treatment,endows the resulting NiCoS_(2)/rGO composite with the advantages:well-dispersed NiCoS_(2) nanoparticles,dualsided rGO support,as well as a large specific surface area of 119.4 m^(2)·g^(-1) and meso-/macroporous size distribution.The NiCoS_(2)/rGO electrocatalyst exhibits an overpotential of 273 mV at 10 mA·cm^(-2) and a good stability of 24 h,which outperform those of the counterparts of NiS_(2)/rGO and CoS_(2)/rGO.The results of electrochemical active surface area and electrochemical impedance spectra experimentally provide convincing rationales of the information of active sites and good conductivity,both underpin the enhanced electrocatalytic performances.
基金the National Natural Science Foundation of China(No.51803130)China Postdoctoral Science Foundation(No.2018M640915)+1 种基金Sichuan Science and Technology Program(No.2019JDRC010)Fundamental Research Funds for Central Universities.
文摘Adding fumed silica(Si0_(2))has been considered as an effective method for tailoring the phase morphology and performance of elastomer-toughened plastic binary blends.It has been demonstrated that the selective distribution of SiO_(2) plays a decisive role in the mechanical properties of plastic/elastomer/SiO_(2)nanocomposites,especially for the impact toughness.In this work,we aim to illuminate the role of specific surface area in controlling their selective distribution of fumed SiO_(2) and consequent mechanical properties of plastic/elastomer binary blends.Three types of SiO_(2) with different specific surface areas were incorporated into polylactide/ethylene-co-vinyl-acetate(PLA/EVA)model blends by melt blending directly.It was found that the selective distribution of SiO_(2) is largely determined by their specific surface areas,i.e.SiO_(2) nanoparticles with low specific surface area has a stronger tendency to be located at the interface between PLA matrix and EVA dispersed phase as compared to those with high specific surface area.The specific surface area-dependent interfacial selective distribution of SiO_(2) is mainly attributed to the extent of increased viscosity of EVA dispersed phase in which SiO_(2)nanoparticles are initially dispersed and resultant migration rate of SiO_(2) nanoparticles.The interfacial localized SiO_(2) nanoparticles induce an obvious enhancement in the impact toughness with strength and modulus well maintained.More importantly,in the case of the same interfacial distribution,toughening efficiency is increased with the specific surface area of SiO_(2).Therefore,this is an optimum specific surface area of SiO_(2) for the toughening.This work not only provides a novel way to manipulate the selective distribution of SiO_(2) in elastomer-toughened plastic blends toward high-performance,but also gives a deep insight into the role of interfacial localized nanoparticles in the toughening mechanism.
基金financially supported by the National Natural Science Foundation of China(Nos.21776147,21606140,61604086,and 21905153)the Qingdao Municipal Science and Technology Bureau,China(19-6-1-91-nsh)+2 种基金the International Science&Technology Cooperation Program of China(No.2014DFA60150)the Department of Science and Technology of Shandong Province(Nos.ZR2018BB066 and 2016GGX104010)the Chemcloudcomputing of National Supercomputing Center in Shenzhen(Shenzhen CloudComputing Center)。
文摘In this work,a facile"carbonization-activation"strategy is developed to synthesize N,P-codoped hierarchical porous carbon.Phosphoric acid is innovatively introduced during the hydrothermal process to achieve in-situ P doping as well as create abundant pores,and the employment of sodamide is of vital importance to simultaneously serve as activating agent and N-source to succeed a high-level N doping.Thus,the obtained samples exhibit a unique three-dimensional hierarchical structure with an ultra-high specific surface area(3646 m^(2)g^(-1))and ultra-high N-doping level(9.81 at.%).Computational analyses confirm that N,P co-doping and higher N content can enhance active sites and widen potential differences of carbon materials to improve their capacitance.The as-prepared carbon materials demonstrate superior electrochemical performances,such as an ultra-high capacitance of 586 Fg^(-1)at 1 Ag^(-1),a superior rate capability of 409 Fg^(-1)at 20 Ag^(-1),and excellent long-term stability of 97%capacitance retention after10,000 cycles in 6 M KOH.Moreover,an assembled symmetric supercapacitor delivers a high energy density of 28.1 Wh kg^(-1)at the power density of 450 W kg^(-1)in 1 M Na_(2)SO_(4),demonstrating a great potential for applications in supercapacitors.
基金support by National Basic Research Program of China(No.2014CB748500)National Natural Science Foundation of China(Nos.51578239,51322805)
文摘An improved biosorbent of thiourea modified chitosan microsphere(TMCM) with high specific surface,favorable mechanical strength and excellent adsorption performance had been synthesized via microfluidic technology. Polyethylene glycol was used as a significant component added in aqueous solution of chitosan to produce such microspheres through droplets forming, chemical crosslinking and pores creating. For the improvement of adsorption capacity, thiourea was considered as an excellent choice in increasing amino functional group by graft modification. The SEM, FTIR and EDS were employed to detect distinct features of TMCM. Copper(Ⅱ) was used to test the adsorption performance of TMCM. The experimental results indicated that TMCM exhibited higher adsorption capacity(q_e= 60.6 mg g_(-1)) and faster adsorption rate than that non-modified chitosan microsphere(NMCM).The adsorption kinetic was described well by the pseudo-second order kinetic model, which suggested that chemical adsorption along with electrons transferring was dominant in adsorption process.
基金the National Key Research and Development Program of China(2021YFE0104900)the National Natural Science Foundation of China(51906247)+1 种基金Hunan Provincial Natural Science Foundation of China(2022JJ20064)the Science and Technology Innovation Program of Hunan Province(2021RC4005).
文摘Biochar produced from pyrolysis of biomass has been developed as a platform carbonaceous material that can be used in various applications.The specific surface area(SSA)and functionalities such as N-containing functional groups of biochar are the most significant properties determining the application performance of biochar as a carbon material in various areas,such as removal of pollutants,adsorption of CO_(2)and H2,catalysis,and energy storage.Producing biochar with preferable SSA and N functional groups is among the frontiers to engineer biochar materials.This study attempted to build machine learning models to predict and optimize specific surface area of biochar(SSA-char),N content of biochar(N-char),and yield of biochar(Yield-char)individually or simultaneously,by using elemental,proximate,and biochemical compositions of biomass and pyrolysis conditions as input variables.The predictions of Yield-char,N-char,and SSA-char were compared by using random forest(RF)and gradient boosting regression(GBR)models.GBR outperformed RF for most predictions.When input parameters included elemental and proximate compositions as well as pyrolysis conditions,the test R^(2) values for the single-target and multi-target GBR models were 0.90-0.95 except for the two-target prediction of Yield-char and SSA-char which had a test R^(2) of 0.84 and the three-target prediction model which had a test R^(2) of 0.81.As indicated by the Pearson correlation coefficient between variables and the feature importance of these GBR models,the top influencing factors toward predicting three targets were specified as follows:pyrolysis temperature,residence time,and fixed carbon for Yield-char;N and ash for N-char;ash and pyrolysis temperature for SSA-char.The effects of these parameters on three targets were different,but the trade-offs of these three were balanced during multi-target ML prediction and optimization.The optimum solutions were then experimentally verified,which opens a new way for designing smart biochar with target properties and oriented application potential.
基金funded by National Natural Science Foundation of China grant number 51403210.
文摘A facile synthesis procedure is proposed to prepare homogeneous Zr and Ti co-doped SBA-15(Zr-Ti-SBA-15)with high specific surface area of 876.0m2 g−1.Based on“masking mechanism”from tanning,lactic acid was used as masking agent to obtain the uniform distribution of Zr and Ti species in the SBA-15 framework.The obtained materials were characterized by powder X-ray diffraction(XRD),nitrogen adsorption-desorption isotherms,scanning electron microscope(SEM),transmission electron microscope(TEM)and X-ray photoelectron(XPS).The results reveal that in mesoporous materials,the presence of lactic acid gives rise to the uniform distribution of Zr and Ti species.The adsorption equilibrium and kinetic studies of Zr-Ti-SBA-15 materials show that the adsorption process conforms to the Langmuir isotherm and pseudo-second-order kinetic model,respectively.Regenerational experiments show that the Zr-Ti-SBA-15 displays a significant adsorption ability for methylene blue(MB)(up to 291.6 mg/g),along with good reusability,indicating promising potentials of commercialization.Methodologically,this work provides a wide range of possibilities for further development of SBA-15 based on bimetallic and sewage disposal.
文摘A series of alumina samples were prepared using β-cyclodextrin as the non-surfactant template. These samples were characterized by XRD, BET and TEM. The results showed that the alumina samples prepared using β-cyclodextrin template had the higher surface areas (124-484 m^2/g), larger pore volumes (0.7-1.27 mL/g) and more thermal stability than samples prepared without using β-cyclodextrin.
基金financially supported by the National Natural Science Foundation of China(Nos.22179123 and52002138)Taishan Scholar Program of Shandong Province+1 种基金China(No.tsqn202211048)the Fundamental Research Funds for the Central Universities(Nos.202262010 and 862201013190)。
文摘Potassium-ion hybrid capacitors(PIHCs)are widely regarded as highly promising energy storage devi-ces,due to their exceptional energy density,impressive power density,and abundant potassium resources.Unfor-tunately,restricted by the inherent capacitive storage mechanism,the carbon cathodes possess a much lower specific capacity than battery-type anodes.Therefore,designing high-performance carbon cathodes is extremely urgent for the development of PIHCs.Herein,N,O co-doped porous carbon(NOPC)was fabricated through the NaCl hard template method and combined KOH/melamine chemical activation technique,displaying the characteris-tics of abundant N/O content(4.7 at%/16.9 at%),ultrahigh specific surface area(3092 m^(2)g^(-1))and hierarchical pore network.The designed NOPC cathode delivers a high specific capacity(164.4 mAh.g^(-1)at 0.05 A.g^(-1))and superior cyclability(95.1%retention ratio at 2 A·g^(-1)over 2500 cycles).Notably,the adjustable ratio of micropores to mesopores facilitates the achievement of the optimal bal-ance between capacity and rate capability.Moreover,the pseudocapacitance can be further augmented through the incorporation of N/O functional groups.As expected,the graphitel/NOPC based PIHC possesses_a high energy density of 113 Wh.kg-at 747 W.kg^(-1)and excellent capacity retention of 84.4%fter 400 cycles at 1.0 A·g^(-1).This work introduces a novel strategy for designing carbon cathodes that enhances the electrochemical performance of PIHCs.
基金General Project of Chongqing Technology Innovation and Application Demonstration(Social People s Livelihood)(cstc2018jscx-msybX0215)Science and Technology Planning Project of Kaizhou District,Chongqing City(KZKJ-2020-J-10).
文摘[Objectives]This study was conducted to explore the differences in physicochemical properties and surface properties of biochar from different sources.[Methods]Four kinds of materials including rice husk and corn straw were prepared at 450℃by the limited-oxygen program temperature control method into biochar,and the differences in physicochemical properties and surface properties of the biochar from different sources were studied.[Results]All four kinds of biochar were alkaline(pH=8.7-10.0).Corn straw biochar had the highest organic carbon content(653.6 g/kg),while rice husk biochar had the lowest organic carbon content(486.1 g/kg).Corn straw biochar had the highest nitrogen content(2.7%),while rice husk biochar had the lowest nitrogen content(0.75%).Corn straw biochar had the highest total phosphorus content(5.64 g/kg),while rice husk biochar had the lowest total phosphorus content(1.1 g/kg).Rice straw biochar had the highest total potassium content(53.1 g/kg),while rice husk biochar had the lowest total potassium content(10.6 g/kg).The four types of biochar were all porous,but their pore structure sizes and shapes were different to certain degrees.The order of the specific surface areas of the four types of biochar was rice stalk biochar>corn stalk biochar>wheat stalk biochar>rice husk biochar;the order of the pore volumes was rice stalk biochar>corn stalk biochar>wheat stalk biochar Charcoal>rice husk biochar;and the pore sizes ranked as wheat stalk biochar>corn stalk biochar>rice husk biochar>rice stalk biochar.The biochar from different sources ranked according to the comprehensive evaluation of all indicators as corn straw biochar>wheat straw biochar>rice straw biochar>rice husk biochar.[Conclusions]This study provides reference data for the preparation process of biochar from industrial and agricultural wastes and its application and promotion.
基金supported by the National Natural Science Foundation of China(No.51472220 and No.51872265)Collaborative Innovation Major Special Project of Zhengzhou(No.20XTZX12025)。
文摘To meet the emission standard of nitrogen oxides(NOx)in the flue gas of batch furnaces through dry adsorption,a calcium-silica inorganic adsorbent was prepared with limestone and quartz as raw materials.Sample Cu-BTC 1#was obtained by solvothermal synthesis,drying and purification in vacuum at 120℃using trimesic acid(H3BTC)and copper nitrate trihydrate(Cu(NO_(3))2·3H_(2)O)as raw materials;likewise,sample Cu-BTC 3#was obtained at 200℃.Sample Cu-BTC 2#was obtained by hydrothermal synthesis,drying and purification in air(metal-organic frameworks,1,3,5-benzene tricarboxylic acid copper).The two types of materials were tested in terms of the NO_(2) adsorption,and then the specific surface area,pore volume,NO_(2) adsorption performance,phase composition,microstructure and thermal stability of the adsorbent materials were exploredvia N_(2) physical adsorption-desorption,SEM,XRD and TG characterization.The results show that:(1)the Cu-BTC samples have higher adsorption capacity than the calcium-silica adsorbent,in which sample Cu-BTC 3#has the largest specific surface area and pore volume,thus adsorption capacity for NO_(2);(2)the calcium-silica adsorbent has better thermal stability and lower total mass loss during the entire process than the Cu-BTC samples;sample Cu-BTC 2#has the best thermal stability among the three Cu-BTC samples,and the metal Cu active sites of the Cu-BTC samples can be exposed at least above 150℃.
文摘Aqueous sols and gels of tungstic acid were prepared from Na2WO4 with protonated cation-exchange resin. Nano-tungsten oxide of a microporous lamella was synthesized by means of washing of WO3· 2H2O with distilled water under ultrasonic wave agitation and centrifuging repeatedly, and the specific surface area tended to increase gradually with washing and centrifuging. The sample of centrifuged 7 h has more than 2 times highs specific surface area and more high photocatalytic activity . The mechanisms are also discussed.
文摘Silica aerogels were prepared at ambient drying by using ethanol/trimethylchlorosilane (TMCS)/heptane solution as pore water exchange and surface modification of the wet gel before drying. The obtained silica aerogels exhibit a sponge-like structure with uniform pore size distribution. The effects of heat-treatment on the hydrophobicity, specific surface area and other properties were investigated. The results indicated that the hydrophobicity of silica aerogels could be maintained up to 350℃. With increasing heating temperature, hydrophobicity decreased, and became completely hydrophilic after heat-treatment at 500℃. Brunaueremmitt-teller (BET) surface area results indicated that the specific surface area of silica aerogels increased with increasing heating temperature in the range of 150-500℃. The effects of heat-treatment on the morphology and chemical bonding state of silica aerogels were investigated by scanning electron microscopy (SEM), differential temperature analysis (DTA) and Fourier-transform infrared spectroscopy (FT-IR).
基金support from the Ministry of Economy, Trade, and Industry (METI) of Japanfunding support from Postgraduate Research & Practice Innovation Program of Jiangsu Province, China (Grant No. KYCX21_0122)
文摘Kozeny-Carman(KC) equation is a well-known relation between hydraulic conductivity and pore properties in porous material. The applications of KC equation to predicting saturated hydraulic conductivities of sands and non-expansive soils are well documented. However, KC equation is incapable of predicting saturated hydraulic conductivity of expansive soil(e.g. bentonite) well. Based on a new dualpore system, this study modified KC equation for improving the prediction of saturated hydraulic conductivities of bentonites. In this study, an assumption that inter-layer space(micropore) has limited effect on fluid flow performance of compacted bentonite was adopted. The critical parameters including total porosity and total tortuosity in conventional KC equation were replaced by macroporosity and tortuosity of macropore, respectively. Macroporosity and microporosity were calculated by basal spacing of compacted bentonite, which was estimated by assuming that specific surface area is changeable during saturation process. A comprehensive comparison of bentonite’s saturated hydraulic conductivity predictions, including modified KC equation proposed in this study, conventional KC equation, and prediction method based on diffuse double layer(DDL) theory, was carried out. It was found that the predicted saturated hydraulic conductivity of bentonites calculated using modified KC equation fitted the experimental data better than others to a certain extent.
基金Peng Wang and Xiaohuan Qi contributed equally to this study.This study was supported by the National Key Research and Development Program(Grant No.2016YFB0901600)National Natural Science Foundation of China(Grant Nos.21801247,51672295,51972326,and 21871008)the Key Research Program of Frontier Chinese Academy of Sciences(Grant No.QYZDJ-SSW-JSC013).
文摘Large surface area,high conductivity,and rich active site of carbon electrode materials are necessary characteristics for energy storage devices.However,high conductivity and high nitrogen doping of carbon electrode materials are difficult to coordinate.Here,a facile method via the carbonization of nitrogen-containing Schiff base polymer has been developed to prepare high conductivity and high nitrogen-doped hierarchical porous carbon.The organic components with a benzene ring structure in the polymer promote the formation of more sp^(2)-graphitized carbon,which is beneficial for the improvement of electrical conductivity.Nitrogen-doped hierarchical porous carbon calcined at 900℃ under the NH3 atmosphere possesses high nitrogen content of 7.48 at%,a large specific surface area of 1613.2m2/g,and high electrical conductivity of 2.7 S/cm.As electrode materials in an aqueous-based supercapacitor,nitrogen-doped hierarchical porous carbon exhibits superior specific capacitance of 385 F/g at 1 A/g as well as excellent rate performance(242 and 215 F/g at a current density of 100 and 200 A/g,respectively).In addition,the specific capacitance of electrode measured in a two-electrode system is 335 F/g at 1 A/g,and the long-term cycling stability can be achieved with more than 94%initial capacitance after 10000 cycles.The constructed symmetric supercapacitor delivers high energy density and high power density.The outstanding electrochemical performances combined with the novel and scalable synthetic approach make the nitrogen‐doped hierarchical porous carbon potential electrode material for electrochemical devices.