Designing highly efficient Pt-free electrocatalysts with low overpotential for an alkaline hydrogen evolution reaction(HER)remains a significant challenge.Here,a novel and efficient cobalt(Co),ruthenium(Ru)bimetallic ...Designing highly efficient Pt-free electrocatalysts with low overpotential for an alkaline hydrogen evolution reaction(HER)remains a significant challenge.Here,a novel and efficient cobalt(Co),ruthenium(Ru)bimetallic electrocatalyst composed of CoRu nanoalloy decorated on the N-doped carbon nanotubes(CoRu@N-CNTs),was prepared by reacting fullerenol with melamine via hydrothermal treatment and followed by pyrolysis.Benefiting from the electronic communication between Co and Ru sites,the as-obtained CoRu@N-CNTs catalyst exhibited superior electrocatalytic HER activity.To deliver a current density of 10 mA·cm^(-2),it required an overpotential of merely 19 mV along with a Tafel slope of 26.19 mV·dec^(-1)in 1 mol·L^(-1)potassium hydroxide(KOH)solution,outperforming the benchmark Pt/C catalyst.The present work would pave a new way towards the design and construction of an efficient electrocatalyst for energy storage and conversion.展开更多
The electrolysis of water powered by renewable energy sources offers a promising method of"green hydrogen"production,which is considered to be at the heart of future carbon-neutral energy systems.In the past...The electrolysis of water powered by renewable energy sources offers a promising method of"green hydrogen"production,which is considered to be at the heart of future carbon-neutral energy systems.In the past decades,researchers have reported a number of hydrogen evolution reaction(HER)electrocatalysts with activity comparable to that of commercial Pt/C,but most of them are tested within a small current density range,typically no more than 500 mA cm^(-2).To realize the industrial application of hydrogen production from water electrolysis,it is essential to develop high-efficiency HER electrocatalysts at high current density(HCD≥500 mA cm^(-2)).Nevertheless,it remains challenging and significant to rational design HCD electrocatalysts for HER.In this paper,the design strategy of HCD electrocatalysts is discussed,and some HCD electrocatalysts for HER are reviewed in seven categories(alloy,metal oxide,metal hydroxide,metal sulfide/selenide,metal nitride,metal phosphide and other derived electrocatalysts).At the end of this article,we also pro-pose some viewpoints and prospects for the future development and research directions of HCD electrocatalysts for HER.展开更多
An immobilized Cu2O/g-C3N4 heterojunction film was successfully made on an FTO substrate by electrophoretic deposition of g-C3N4 on a Cu2O thin film.The photoelectrochemical(PEC) performance for water splitting by t...An immobilized Cu2O/g-C3N4 heterojunction film was successfully made on an FTO substrate by electrophoretic deposition of g-C3N4 on a Cu2O thin film.The photoelectrochemical(PEC) performance for water splitting by the Cu2O/g-C3N4 film was better than pure g-C3N4 and pure Cu2O film.Under-0.4 V external bias and visible light irradiation,the photocurrent density and PEC hydrogen evolution efficiency of the optimized Cu2O/g-C3N4 film was-1.38 mA/cm^2 and 0.48 mL h^-1 cm^-2,respectively.The enhanced PEC performance of Cu2O/g-C3N4 was attributed to the synergistic effect of light coupling and a matching energy band structure between g-C3N4 and Cu2O as well as the external bias.展开更多
A novel composition of AlLi/NaBH4 mixture activated by common Ni powder in water for hydrogen generation was investigated. The composition presents good hydrogen generation performance and an optimized Al-10% Li-10% N...A novel composition of AlLi/NaBH4 mixture activated by common Ni powder in water for hydrogen generation was investigated. The composition presents good hydrogen generation performance and an optimized Al-10% Li-10% Ni/NaBH4 mixture (mass ratio of 3:1) generates 1540 mL/g hydrogen with 96% efficiency at 333 K. Ni powder exhibits dual catalytic effects on the hydrolysis of AlLi/NaBH4 mixture due to the formation of Ni2B in the hydrolysis process. The Ni2B deposited on aluminum surface could act as a cathode of a micro galvanic couple. Ni2B/Al(OH)3 also has a synergistic effect on NaBH4 hydrolysis. Good hydrogen generation performance with stable pH value of hydrolysis byproduct Al(OH)3/NaBO2-2H2O was obtained with successive additions of Al-Li-Ni /NaBH4 mixture into fixed water.展开更多
The mixture of CaHPO 4·2H 2O and CaCO 3 was ground in an aqueous system under appropriate conditions to investigate the mechanochemical reaction for the synthesis of crystalline hydroxyapatite (HA) powder. Hyd...The mixture of CaHPO 4·2H 2O and CaCO 3 was ground in an aqueous system under appropriate conditions to investigate the mechanochemical reaction for the synthesis of crystalline hydroxyapatite (HA) powder. Hydroxyapatite of high crystallinity powder including trace Ca 10 (PO 4) 6CO 3(OH) and Ca 9HPO 4(PO 4) 6OH can be synthesized by mechanical activation without further thermal treatment at a high temperature. The synthesis reaction during the grinding process was almost completed within 1h. The as-ground powder exhibits a particle distribution of 20-100nm in size with a spherical or rodlike morphology. The composition and degree of crystallinity of the mechanochemical synthesized hydroxyapatite powders were coincident with the cement-type hydroxyapatite.展开更多
Mg-Al-Pb alloy is one of the newly developed materials for the seawater activated batteries. As-cast Mg-6Al-5Pb and Mg-6Al-5Pb-0.5Mn alloys with different additions of Al-15%Mn (mass fraction), Al-30%Mn and Al-50%Mn...Mg-Al-Pb alloy is one of the newly developed materials for the seawater activated batteries. As-cast Mg-6Al-5Pb and Mg-6Al-5Pb-0.5Mn alloys with different additions of Al-15%Mn (mass fraction), Al-30%Mn and Al-50%Mn master alloys were prepared by melting and casting. Their microstructures were observed by optical microscopy and scanning electron microscopy. The electrochemical properties, hydrogen evolution and mass loss of Mg-6Al-5Pb-0.5Mn alloys were studied. The results show that Mg-6Al-5Pb-0.5Mn alloy added with Al-50%Mn master alloy provides more negative corrosion average potential (-1.66 V), smaller corrosion current density (7 μm/cm2) and lower free corrosion rate (0.51 mg·cm-2·h-1) than other alloys. This is probably attributed to the presence of Al11Mn4 phase, which facilitates the self-peeling of corrosion products and enlarges the electrochemical reaction area as well as enhances the electrochemical activity.展开更多
Mg-Al-Pb alloy is a good candidate for the anode material of magnesium seawater battery. For improving the low current utilization efficiency of Mg-Al-Pb alloy, the influence of Ce on the microstructures and electroch...Mg-Al-Pb alloy is a good candidate for the anode material of magnesium seawater battery. For improving the low current utilization efficiency of Mg-Al-Pb alloy, the influence of Ce on the microstructures and electrochemical corrosion properties in a 3.5% NaCl solution was investigated using scanning electron microscope and electrochemical measurements. The results indicate that Ce refines the grain structure of Mg-Al-Pb alloy. The formation of strip Al11Ce3 second phase promotes the uniform distribution of Mg17Al12 phase in Mg-Al-Pb-Ce alloy. The addition of cerium accelerates the discharge activity of Mg-Al-Pb alloy. Due to a large number of cathodic Al11Ce3 and MglyAla2 phases, Ce promotes the micro-galvanic corrosion and leads to larger corrosion current density and hydrogen evolution rate in Mg-Al-Pb-Ce alloy than those in Mg-Al-Pb alloy. However, Mg-Al-Pb alloy expresses smaller utilization efficiency than Mg-Al-Pb-Ce alloy because of grain detachment.展开更多
[Objective] This study was to explore the effects of dilute acid hydrolysis on fermentative biohydrogen production capacity of maize stalk. [Method] Using maize stalks subjected to mechanical disintegration,steam expl...[Objective] This study was to explore the effects of dilute acid hydrolysis on fermentative biohydrogen production capacity of maize stalk. [Method] Using maize stalks subjected to mechanical disintegration,steam explosion and dilute acid hydrolysis as experimental materials,we measured and analyzed the effects of different treatments and particle size of maize stalk were analyzed. [Result] The optimal fermentative biohydrogen production was found under following parameters:pretreatment of 0.8% dilute H2SO4 following steam explosion,particle size of maize stalk of 0.425-0.850 mm,liquid-solid ratio [0.8% H2SO4 (M):stalk (W)] of 10:1. [Conclusion] Post steam explosion,dilute 0.8% dilute H2SO4 intensified hydrolysis on maize stalk could produce fermentative biohydrogen production capacity.展开更多
[Objective] The effects of yttrium nitrate (YNO3) on biomass and antioxi- dant systems of paddy rice (Yttrium (Y); Oxidative stress; Dismutases (SOD); Per- oxidases (POD), Catalases (CAT), Paddy rice (Trit...[Objective] The effects of yttrium nitrate (YNO3) on biomass and antioxi- dant systems of paddy rice (Yttrium (Y); Oxidative stress; Dismutases (SOD); Per- oxidases (POD), Catalases (CAT), Paddy rice (Triticum aestivum)) together with the occurrences of Y in soils were investigated to assess its ecotoxicological effects on plant. [Method]Y solutions with various concentrations were sprinkled on soil sam- ples, which were well mixed and then put into culture dishes to culture paddy rice seeds for further evaluation. [Result] The results indicated that 25-100 mg/kg Y treatments significantly increased the biomass (total weight, root weight, shoot weight and leaf weight), chlorophyll (CHL) content and protein content of paddy rice, whereas 200-800 mg/kg Y treatments had a converse effect. Similarly, biomarker for the antioxidant systems including superoxide dismutases (SOD), peroxidases (POD) and catalases (CAT) all exhibited similar trends in both shoots and roots of paddy rice. At the same time, the malonaldehyde (MDA) content increased at from 25 to 100 mg/kg and decreased with concentrations of Y from 100 to 800 mg/kg in both shoots and roots of paddy rice. This indicated that Y could stimulate the growth of plant at low concentration, but inhibit the growth at relatively high concen- tration. [Conclusion] The levels of Y were 641+49, 328_+16 and 473_+40 mg/kg in soils collected from mining area, farmland and navel orange orchard respectively. The levels of Y in the investigated area were higher than the benefit level (100 mg/kg), which could cause low biomass as well as low activity of SOD, POD and CAT in paddy rice. Therefore, a more careful use of Y is necessary in crop management.展开更多
We investigated high catalytic activity of Ni/HZSM-5 catalysts synthesized by the impregnation method, which was successfully applied for low-temperature steam reforming of bio-oil. The influences of the catalyst comp...We investigated high catalytic activity of Ni/HZSM-5 catalysts synthesized by the impregnation method, which was successfully applied for low-temperature steam reforming of bio-oil. The influences of the catalyst composition, reforming temperature and the molar ratio of steam to carbon fed on the stream reforming process of bio-oil over the Ni/HZSM-5 catalysts were investigated in the reforming reactor. The promoting effects of current passing through the catalyst on the bio-oil reforming were also studied using the electrochemical catalytic reforming approach. By comparing Ni/HZSM-5 with commonly used Ni/Al2O3 catalysts, the Ni2O/ZSM catalyst with Ni-loading content of about 20% on the HZSM-5 support showed the highest catalytic activity. Even at 450 ℃, the hydrogen yield of about 90% with a near complete conversion of bio-oil was obtained using the Ni2O/ZSM catalyst. It was found that the performance of the bio-oil reforming was remarkably enhanced by the HZSM-5 supporter and the current through the catalyst. The features of the Ni/HZSM-5 catalysts were also investigated via X-ray diffraction, inductively coupled plasma and atomic emission spectroscopy, hydrogen temperature-programmed reduction, and Brunauer-Emmett-Teller methods.展开更多
All-atom molecular dynamics (MD) simulation and the NMR spectra are used to investigate the interactions in N-glycylglycine aqueous solution. Different types of atoms exhibit different capability in forming hydrogen...All-atom molecular dynamics (MD) simulation and the NMR spectra are used to investigate the interactions in N-glycylglycine aqueous solution. Different types of atoms exhibit different capability in forming hydrogen bonds by the radial distribution function analysis. Some typical dominant aggregates are found in different types of hydrogen bonds by the statistical hydrogen-bonding network. Moreover, temperature-dependent NMR are used to compare with the results of the MD simulations. The chemical shifts of the three hydrogen atoms all decrease with the temperature increasing which reveals that the hydrogen bonds are dominant in the glycylglycine aqueous solution. And the NMR results show agreement with the MD simulations. All-atom MD simulations and NMR spectra are successful in revealing the structures and interactions in the N-glycylglycine-water mixtures.展开更多
An all-atom dimethyl sulfoxide (DMSO) and water model have been used for molecular dynamics simulation. The NMR and IR spectra are also performed to study the structures and interactions in the DMSO-water system. An...An all-atom dimethyl sulfoxide (DMSO) and water model have been used for molecular dynamics simulation. The NMR and IR spectra are also performed to study the structures and interactions in the DMSO-water system. And there are traditional strong hydrogen bonds and weak C-H- ~ ~ O contacts existing in the mixtures according to the analysis of the radial distribution functions. The insight structures in the DMSO-water mixtures can be classified into different regions by the analysis of the hydrogen-bonding network. Interestingly, the molar fraction of DMSO 0.35 is found to be a special concentration by the network. It is the transitional region which is from the water rich region to the DMSO rich region. The stable aggregates of (DMSO)m'S=O…… HW-OW-(H20)n might play a key role in this region. Moreover, the simulation is compared with the chemical shifts in NMR and wavenumbers in IR with concentration dependence. And the statistical results of the average number hydrogen bonds in the MD simulations are in agreement with the experiment data in NMR and IR spectra.展开更多
Molecular dynamics simulations were carried out to study the internal energy and microstructure of potassium dihydrogen phosphates (KDP) solution at different temperatures. The water molecule was treated as a simple...Molecular dynamics simulations were carried out to study the internal energy and microstructure of potassium dihydrogen phosphates (KDP) solution at different temperatures. The water molecule was treated as a simple-point-charge model, while a seven-site model for the dihydrogen phosphate ion was adopted. The internal energy functions and the radial distribution functions of the solution were studied in detail. An unusually large local particle number density fluctuation was observed in the system at saturation temperature. It has been found that the specific heat of oversaturated solution is higher than that of unsaturated solution, which indicates the solution experiences a crystallization process below saturation temperature. The radial distribution function between the oxygen atom of water and the hydrogen atom of the dihydrogen phosphate ion shows a very strong hydrogen bond structure. There are strong interactions between potassium cation and oxygen atom of dihydrogen phosphate ion in KDP solution, and much more ion pairs were formed in saturated solution.展开更多
Low melting point metals(Ga, In, Sn) as alloy elements were used to prepare Al-In-Sn and Al-Ga-In-Sn alloys through mechanical ball milling method. The effects of mass ratio of In to Sn and Ga content on the hydroly...Low melting point metals(Ga, In, Sn) as alloy elements were used to prepare Al-In-Sn and Al-Ga-In-Sn alloys through mechanical ball milling method. The effects of mass ratio of In to Sn and Ga content on the hydrolysis properties of aluminum alloys were investigated. X-ray diffraction(XRD) and scanning electron microscopy(SEM) with energy disperse spectroscopy(EDS) were used to analyze the compositions and morphologies of the obtained Al alloys. The results show that the phase compositions of Al-In-Sn ternary alloys are Al and two intermetallic compounds, In3 Sn and In Sn4. All Al-In-Sn ternary alloys exhibit poor hydrolysis activity at room temperature. Al-In-Sn alloy with the mass ratio of In to Sn equaling 1:4 has the highest hydrogen yield. After Ga is introduced to the ternary alloys, the hydrolysis activity of aluminum alloys at room temperature is greatly improved. It is speculated that the addition of Ga element promotes the formation of defects inside the Al alloys and Ga-In3Sn-In Sn4 eutectic alloys on the alloys surface. Al atoms can be dissolved in this eutectic phase and become the active spots during the hydrolysis process. The small size and uniform distribution of this eutectic phase may be responsible for the enhancement of hydrolysis activity.展开更多
Photocatalytic oxidation of water is a promising method to realize large-scale H2O2 production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO2(anatase) photocatalyst to construc...Photocatalytic oxidation of water is a promising method to realize large-scale H2O2 production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO2(anatase) photocatalyst to construct a simple and environmentally friendly system to achieve simultaneous H2 and H2O2 production. Both H2 and H2O2 are high-value chemicals, and their separation is automatic. Even without the assistance of a sacrificial agent, the system can reach an efficiency of 7410 and 5096 μmol g^-1 h^–1 (first 1 h) for H2 and H2O2, respectively, which is much higher than that of a commercial Pt/TiO2(anatase) system that has a similar morphology. This exceptional activity is attributed to the more favorable two-electron oxidation of water to H2O2, compared with the four-electron oxidation of water to O2.展开更多
The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions f...The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions for preparing well-dispersed nanoparticles were found as follows: 0.4 mol/L NaBH4 was added into solution containing 0.2 mol/L Cu2+, 1.0% gelatin dispersant in mass fraction, and 1.2 mol/L NH3?H2O at pH 12 and 313 K. In addition, a series of experiments were performed to discover the reaction process. NH3?H2O was found to be able to modulate the reaction process. At pH=10, Cu2+ was transformed to Cu(NH3)42+ as precursor after the addition of NH3?H2O, and then Cu(NH3)42+ was reduced by NaBH4 solution. At pH=12, Cu2+ was transformed to Cu(OH)2 as precursor after the addition of NH3?H2O, and Cu(OH)2 was then reduced by NaBH4 solution.展开更多
Searching for low-cost widely applicable electrocatalysts for hydrogen production is very important. Here, 3D self-supported NiS2/MoS2 heterostructures were synthesized via a one-step millisecond- laser-direct-writing...Searching for low-cost widely applicable electrocatalysts for hydrogen production is very important. Here, 3D self-supported NiS2/MoS2 heterostructures were synthesized via a one-step millisecond- laser-direct-writing method;these structures exhibited excellent hydrogen evolution reaction activities over a wide pH range. The current density of 10 mA cm^-2 could be reached at low overpotentials of 98 and 159 mV in alkaline and neutral electrolytes, respectively. Such an outstanding electrocatalytic performance should be attributed to the integration of the 3D self-supported nanostructures, the high conductivity of the framework, and particularly, the incalculable heterointerfaces formed between NiS2 and MoS2. This work provides a new strategy to study interfacial engineering and the mechanism of interface enhancement.展开更多
Sunlight-driven photocatalytic water-splitting for hydrogen(H2)evolution is a desirable strategy to utilize solar energy.However,this strategy is restricted by insufficient light harvesting and high photogenerated ele...Sunlight-driven photocatalytic water-splitting for hydrogen(H2)evolution is a desirable strategy to utilize solar energy.However,this strategy is restricted by insufficient light harvesting and high photogenerated electron-hole recombination rates of TiO2-based photocatalysts.Here,a graphene-modified WO3/TiO2 step-scheme heterojunction(S-scheme heterojunction)composite photocatalyst was fabricated by a facile one-step hydrothermal method.In the ternary composite,TiO2 and WO3 nanoparticles adhered closely to reduced graphene oxide(rGO)and formed a novel S-scheme heterojunction.Moreover,rGO in the composite not only supplied abundant adsorption and catalytically active sites as an ideal support but also promoted electron separation and transfer from the conduction band of TiO2 by forming a Schottky junction between TiO2 and rGO.The positive cooperative effect of the S-scheme heterojunction formed between WO3 and TiO2 and the Schottky heterojunction formed between TiO2 and graphene sheets suppressed the recombination of relatively useful electrons and holes.This effect also enhanced the light harvesting and promoted the reduction reaction at the active sites.Thus,the novel ternary WO3/TiO2/rGO composite demonstrated a remarkably enhanced photocatalytic H2 evolution rate of 245.8μmol g^-1 h^-1,which was approximately 3.5-fold that of pure TiO2.This work not only presents a low-cost graphene-based S-scheme heterojunction photocatalyst that was obtained via a feasible one-step hydrothermal approach to realize highly efficient H2 generation without using noble metals,but also provides new insights into the design of novel heterojunction photocatalysts.展开更多
A lab-scale expanded granular sludge bed (EGSB) reactor was employed to evaluate the feasibility of the hydrogen energy recovery potential from high strength organic wastewater. The results showed that a maximum hyd...A lab-scale expanded granular sludge bed (EGSB) reactor was employed to evaluate the feasibility of the hydrogen energy recovery potential from high strength organic wastewater. The results showed that a maximum hydrogen production rate of 7.43 m^3 H2/m^3 reactor · d and an average hydrogen production rate of 6.44- ms H^2/ms reactor · d were achieved with the hydrogen content of 50% -56% in the biogas during the 90-day operation. At the acidogenic phase, COD removal rate was stable at about 15%. In the steady operation period, the main liquid end products were ethanol and acetic acid, which represented ethanol type fermentation. Among the liquid end products, the concentration percentage of ethanol and acetic acid amounted to 69.5% - 89. 8% and the concentration percentage of ethanol took prominent about 51.7% - 59. 1%, which is better than the utilization of substrate for the methanogenic bacteria. An ethanol type fermentation pathway was suggested in the operation of enlarged industrial continuous hydrogen bio-producing reactors.展开更多
基金supported by the National Natural Science Foundation of China(No.52072226,U22A20144)Key Research and Development Program of Shaanxi(2024GX-YBXM-466)+1 种基金Science and Technology Program of Xi'an,China(22GXFW0013)Science and Technology Program of Weiyang District of Xi'an,China(202315)。
文摘Designing highly efficient Pt-free electrocatalysts with low overpotential for an alkaline hydrogen evolution reaction(HER)remains a significant challenge.Here,a novel and efficient cobalt(Co),ruthenium(Ru)bimetallic electrocatalyst composed of CoRu nanoalloy decorated on the N-doped carbon nanotubes(CoRu@N-CNTs),was prepared by reacting fullerenol with melamine via hydrothermal treatment and followed by pyrolysis.Benefiting from the electronic communication between Co and Ru sites,the as-obtained CoRu@N-CNTs catalyst exhibited superior electrocatalytic HER activity.To deliver a current density of 10 mA·cm^(-2),it required an overpotential of merely 19 mV along with a Tafel slope of 26.19 mV·dec^(-1)in 1 mol·L^(-1)potassium hydroxide(KOH)solution,outperforming the benchmark Pt/C catalyst.The present work would pave a new way towards the design and construction of an efficient electrocatalyst for energy storage and conversion.
文摘The electrolysis of water powered by renewable energy sources offers a promising method of"green hydrogen"production,which is considered to be at the heart of future carbon-neutral energy systems.In the past decades,researchers have reported a number of hydrogen evolution reaction(HER)electrocatalysts with activity comparable to that of commercial Pt/C,but most of them are tested within a small current density range,typically no more than 500 mA cm^(-2).To realize the industrial application of hydrogen production from water electrolysis,it is essential to develop high-efficiency HER electrocatalysts at high current density(HCD≥500 mA cm^(-2)).Nevertheless,it remains challenging and significant to rational design HCD electrocatalysts for HER.In this paper,the design strategy of HCD electrocatalysts is discussed,and some HCD electrocatalysts for HER are reviewed in seven categories(alloy,metal oxide,metal hydroxide,metal sulfide/selenide,metal nitride,metal phosphide and other derived electrocatalysts).At the end of this article,we also pro-pose some viewpoints and prospects for the future development and research directions of HCD electrocatalysts for HER.
基金supported by the National Natural Science Foundation of China (21173088)the Science and Technology Project of Guangdong Province (2014A030312007, 2015A050502012, 2016A010104013)+1 种基金the China Postdoctoral Science Foundation (2016M592493)the Open Research Fund of Hunan Key Laboratory of Applied Environmental Photocatalysis (CCSU-XT-06),Changsha University~~
文摘An immobilized Cu2O/g-C3N4 heterojunction film was successfully made on an FTO substrate by electrophoretic deposition of g-C3N4 on a Cu2O thin film.The photoelectrochemical(PEC) performance for water splitting by the Cu2O/g-C3N4 film was better than pure g-C3N4 and pure Cu2O film.Under-0.4 V external bias and visible light irradiation,the photocurrent density and PEC hydrogen evolution efficiency of the optimized Cu2O/g-C3N4 film was-1.38 mA/cm^2 and 0.48 mL h^-1 cm^-2,respectively.The enhanced PEC performance of Cu2O/g-C3N4 was attributed to the synergistic effect of light coupling and a matching energy band structure between g-C3N4 and Cu2O as well as the external bias.
基金Projects (21003112, 21003111) supported by the National Natural Science Foundation of ChinaProject (Y4090507) supported by the Zhejiang Basic Research Program, China
文摘A novel composition of AlLi/NaBH4 mixture activated by common Ni powder in water for hydrogen generation was investigated. The composition presents good hydrogen generation performance and an optimized Al-10% Li-10% Ni/NaBH4 mixture (mass ratio of 3:1) generates 1540 mL/g hydrogen with 96% efficiency at 333 K. Ni powder exhibits dual catalytic effects on the hydrolysis of AlLi/NaBH4 mixture due to the formation of Ni2B in the hydrolysis process. The Ni2B deposited on aluminum surface could act as a cathode of a micro galvanic couple. Ni2B/Al(OH)3 also has a synergistic effect on NaBH4 hydrolysis. Good hydrogen generation performance with stable pH value of hydrolysis byproduct Al(OH)3/NaBO2-2H2O was obtained with successive additions of Al-Li-Ni /NaBH4 mixture into fixed water.
文摘The mixture of CaHPO 4·2H 2O and CaCO 3 was ground in an aqueous system under appropriate conditions to investigate the mechanochemical reaction for the synthesis of crystalline hydroxyapatite (HA) powder. Hydroxyapatite of high crystallinity powder including trace Ca 10 (PO 4) 6CO 3(OH) and Ca 9HPO 4(PO 4) 6OH can be synthesized by mechanical activation without further thermal treatment at a high temperature. The synthesis reaction during the grinding process was almost completed within 1h. The as-ground powder exhibits a particle distribution of 20-100nm in size with a spherical or rodlike morphology. The composition and degree of crystallinity of the mechanochemical synthesized hydroxyapatite powders were coincident with the cement-type hydroxyapatite.
基金Project(JPPT-115-168)supported by the National Key Science and Technological Project of ChinaProject(51101171)supported by the National Natural Science Foundation of China
文摘Mg-Al-Pb alloy is one of the newly developed materials for the seawater activated batteries. As-cast Mg-6Al-5Pb and Mg-6Al-5Pb-0.5Mn alloys with different additions of Al-15%Mn (mass fraction), Al-30%Mn and Al-50%Mn master alloys were prepared by melting and casting. Their microstructures were observed by optical microscopy and scanning electron microscopy. The electrochemical properties, hydrogen evolution and mass loss of Mg-6Al-5Pb-0.5Mn alloys were studied. The results show that Mg-6Al-5Pb-0.5Mn alloy added with Al-50%Mn master alloy provides more negative corrosion average potential (-1.66 V), smaller corrosion current density (7 μm/cm2) and lower free corrosion rate (0.51 mg·cm-2·h-1) than other alloys. This is probably attributed to the presence of Al11Mn4 phase, which facilitates the self-peeling of corrosion products and enlarges the electrochemical reaction area as well as enhances the electrochemical activity.
基金Project(2015JC3004)supported by Science and Technology Plan Projects of Hunan Province,ChinaProject(51401243)supported by the National Natural Science Foundation of China
文摘Mg-Al-Pb alloy is a good candidate for the anode material of magnesium seawater battery. For improving the low current utilization efficiency of Mg-Al-Pb alloy, the influence of Ce on the microstructures and electrochemical corrosion properties in a 3.5% NaCl solution was investigated using scanning electron microscope and electrochemical measurements. The results indicate that Ce refines the grain structure of Mg-Al-Pb alloy. The formation of strip Al11Ce3 second phase promotes the uniform distribution of Mg17Al12 phase in Mg-Al-Pb-Ce alloy. The addition of cerium accelerates the discharge activity of Mg-Al-Pb alloy. Due to a large number of cathodic Al11Ce3 and MglyAla2 phases, Ce promotes the micro-galvanic corrosion and leads to larger corrosion current density and hydrogen evolution rate in Mg-Al-Pb-Ce alloy than those in Mg-Al-Pb alloy. However, Mg-Al-Pb alloy expresses smaller utilization efficiency than Mg-Al-Pb-Ce alloy because of grain detachment.
基金Supported by National Basic Research Program of China(2006CB708407 2009CB220005)+2 种基金National Natural Science Foun-dation of China (90610001 20871106)Program of 211 Projectfor Zhengzhou University from Ministry of Education~~
文摘[Objective] This study was to explore the effects of dilute acid hydrolysis on fermentative biohydrogen production capacity of maize stalk. [Method] Using maize stalks subjected to mechanical disintegration,steam explosion and dilute acid hydrolysis as experimental materials,we measured and analyzed the effects of different treatments and particle size of maize stalk were analyzed. [Result] The optimal fermentative biohydrogen production was found under following parameters:pretreatment of 0.8% dilute H2SO4 following steam explosion,particle size of maize stalk of 0.425-0.850 mm,liquid-solid ratio [0.8% H2SO4 (M):stalk (W)] of 10:1. [Conclusion] Post steam explosion,dilute 0.8% dilute H2SO4 intensified hydrolysis on maize stalk could produce fermentative biohydrogen production capacity.
基金Supported by the National Natural Science Foundation of China(21067003,51364015)the National High-Tech Research and Development Program of China(2012BAC11B07)the Jiangxi Natural Science Foundation(20114BAB203024)~~
文摘[Objective] The effects of yttrium nitrate (YNO3) on biomass and antioxi- dant systems of paddy rice (Yttrium (Y); Oxidative stress; Dismutases (SOD); Per- oxidases (POD), Catalases (CAT), Paddy rice (Triticum aestivum)) together with the occurrences of Y in soils were investigated to assess its ecotoxicological effects on plant. [Method]Y solutions with various concentrations were sprinkled on soil sam- ples, which were well mixed and then put into culture dishes to culture paddy rice seeds for further evaluation. [Result] The results indicated that 25-100 mg/kg Y treatments significantly increased the biomass (total weight, root weight, shoot weight and leaf weight), chlorophyll (CHL) content and protein content of paddy rice, whereas 200-800 mg/kg Y treatments had a converse effect. Similarly, biomarker for the antioxidant systems including superoxide dismutases (SOD), peroxidases (POD) and catalases (CAT) all exhibited similar trends in both shoots and roots of paddy rice. At the same time, the malonaldehyde (MDA) content increased at from 25 to 100 mg/kg and decreased with concentrations of Y from 100 to 800 mg/kg in both shoots and roots of paddy rice. This indicated that Y could stimulate the growth of plant at low concentration, but inhibit the growth at relatively high concen- tration. [Conclusion] The levels of Y were 641+49, 328_+16 and 473_+40 mg/kg in soils collected from mining area, farmland and navel orange orchard respectively. The levels of Y in the investigated area were higher than the benefit level (100 mg/kg), which could cause low biomass as well as low activity of SOD, POD and CAT in paddy rice. Therefore, a more careful use of Y is necessary in crop management.
基金ACKNOWLEDGMENTS This work is supported by the National High Tech Research and Development Program (No.2009AA05Z435), the National Basic Research Program of Ministry of Science and Technology of China (No.2007CB210206), and the General Program of the National Natural Science Foundation of China (No.50772107).
文摘We investigated high catalytic activity of Ni/HZSM-5 catalysts synthesized by the impregnation method, which was successfully applied for low-temperature steam reforming of bio-oil. The influences of the catalyst composition, reforming temperature and the molar ratio of steam to carbon fed on the stream reforming process of bio-oil over the Ni/HZSM-5 catalysts were investigated in the reforming reactor. The promoting effects of current passing through the catalyst on the bio-oil reforming were also studied using the electrochemical catalytic reforming approach. By comparing Ni/HZSM-5 with commonly used Ni/Al2O3 catalysts, the Ni2O/ZSM catalyst with Ni-loading content of about 20% on the HZSM-5 support showed the highest catalytic activity. Even at 450 ℃, the hydrogen yield of about 90% with a near complete conversion of bio-oil was obtained using the Ni2O/ZSM catalyst. It was found that the performance of the bio-oil reforming was remarkably enhanced by the HZSM-5 supporter and the current through the catalyst. The features of the Ni/HZSM-5 catalysts were also investigated via X-ray diffraction, inductively coupled plasma and atomic emission spectroscopy, hydrogen temperature-programmed reduction, and Brunauer-Emmett-Teller methods.
文摘All-atom molecular dynamics (MD) simulation and the NMR spectra are used to investigate the interactions in N-glycylglycine aqueous solution. Different types of atoms exhibit different capability in forming hydrogen bonds by the radial distribution function analysis. Some typical dominant aggregates are found in different types of hydrogen bonds by the statistical hydrogen-bonding network. Moreover, temperature-dependent NMR are used to compare with the results of the MD simulations. The chemical shifts of the three hydrogen atoms all decrease with the temperature increasing which reveals that the hydrogen bonds are dominant in the glycylglycine aqueous solution. And the NMR results show agreement with the MD simulations. All-atom MD simulations and NMR spectra are successful in revealing the structures and interactions in the N-glycylglycine-water mixtures.
文摘An all-atom dimethyl sulfoxide (DMSO) and water model have been used for molecular dynamics simulation. The NMR and IR spectra are also performed to study the structures and interactions in the DMSO-water system. And there are traditional strong hydrogen bonds and weak C-H- ~ ~ O contacts existing in the mixtures according to the analysis of the radial distribution functions. The insight structures in the DMSO-water mixtures can be classified into different regions by the analysis of the hydrogen-bonding network. Interestingly, the molar fraction of DMSO 0.35 is found to be a special concentration by the network. It is the transitional region which is from the water rich region to the DMSO rich region. The stable aggregates of (DMSO)m'S=O…… HW-OW-(H20)n might play a key role in this region. Moreover, the simulation is compared with the chemical shifts in NMR and wavenumbers in IR with concentration dependence. And the statistical results of the average number hydrogen bonds in the MD simulations are in agreement with the experiment data in NMR and IR spectra.
文摘Molecular dynamics simulations were carried out to study the internal energy and microstructure of potassium dihydrogen phosphates (KDP) solution at different temperatures. The water molecule was treated as a simple-point-charge model, while a seven-site model for the dihydrogen phosphate ion was adopted. The internal energy functions and the radial distribution functions of the solution were studied in detail. An unusually large local particle number density fluctuation was observed in the system at saturation temperature. It has been found that the specific heat of oversaturated solution is higher than that of unsaturated solution, which indicates the solution experiences a crystallization process below saturation temperature. The radial distribution function between the oxygen atom of water and the hydrogen atom of the dihydrogen phosphate ion shows a very strong hydrogen bond structure. There are strong interactions between potassium cation and oxygen atom of dihydrogen phosphate ion in KDP solution, and much more ion pairs were formed in saturated solution.
基金Project(2010CB635107) supported by the Major State Basic Research Development Program of ChinaProjects(51202064,51472081) supported by the National Natural Science Foundation of China+2 种基金Project(2013CFA085) supported by the Natural Science Foundation of Hubei Province,ChinaProject(2013070104010016) supported by Wuhan Youth Chenguang Program of Science and Technology,ChinaProject([2013]2-22) supported by the Open Fund of Key Laboratory of Green Materials for Light Industry of Hubei Province,China
文摘Low melting point metals(Ga, In, Sn) as alloy elements were used to prepare Al-In-Sn and Al-Ga-In-Sn alloys through mechanical ball milling method. The effects of mass ratio of In to Sn and Ga content on the hydrolysis properties of aluminum alloys were investigated. X-ray diffraction(XRD) and scanning electron microscopy(SEM) with energy disperse spectroscopy(EDS) were used to analyze the compositions and morphologies of the obtained Al alloys. The results show that the phase compositions of Al-In-Sn ternary alloys are Al and two intermetallic compounds, In3 Sn and In Sn4. All Al-In-Sn ternary alloys exhibit poor hydrolysis activity at room temperature. Al-In-Sn alloy with the mass ratio of In to Sn equaling 1:4 has the highest hydrogen yield. After Ga is introduced to the ternary alloys, the hydrolysis activity of aluminum alloys at room temperature is greatly improved. It is speculated that the addition of Ga element promotes the formation of defects inside the Al alloys and Ga-In3Sn-In Sn4 eutectic alloys on the alloys surface. Al atoms can be dissolved in this eutectic phase and become the active spots during the hydrolysis process. The small size and uniform distribution of this eutectic phase may be responsible for the enhancement of hydrolysis activity.
基金supported by the National Natural Science Foundation of China(21703046)the National Key R&D of China(2016YFF0203803 and 2016YFA0200902)~~
文摘Photocatalytic oxidation of water is a promising method to realize large-scale H2O2 production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO2(anatase) photocatalyst to construct a simple and environmentally friendly system to achieve simultaneous H2 and H2O2 production. Both H2 and H2O2 are high-value chemicals, and their separation is automatic. Even without the assistance of a sacrificial agent, the system can reach an efficiency of 7410 and 5096 μmol g^-1 h^–1 (first 1 h) for H2 and H2O2, respectively, which is much higher than that of a commercial Pt/TiO2(anatase) system that has a similar morphology. This exceptional activity is attributed to the more favorable two-electron oxidation of water to H2O2, compared with the four-electron oxidation of water to O2.
文摘The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions for preparing well-dispersed nanoparticles were found as follows: 0.4 mol/L NaBH4 was added into solution containing 0.2 mol/L Cu2+, 1.0% gelatin dispersant in mass fraction, and 1.2 mol/L NH3?H2O at pH 12 and 313 K. In addition, a series of experiments were performed to discover the reaction process. NH3?H2O was found to be able to modulate the reaction process. At pH=10, Cu2+ was transformed to Cu(NH3)42+ as precursor after the addition of NH3?H2O, and then Cu(NH3)42+ was reduced by NaBH4 solution. At pH=12, Cu2+ was transformed to Cu(OH)2 as precursor after the addition of NH3?H2O, and Cu(OH)2 was then reduced by NaBH4 solution.
基金financially supported by the National Natural Science Foundation of China(51572188 and 51822106)~~
文摘Searching for low-cost widely applicable electrocatalysts for hydrogen production is very important. Here, 3D self-supported NiS2/MoS2 heterostructures were synthesized via a one-step millisecond- laser-direct-writing method;these structures exhibited excellent hydrogen evolution reaction activities over a wide pH range. The current density of 10 mA cm^-2 could be reached at low overpotentials of 98 and 159 mV in alkaline and neutral electrolytes, respectively. Such an outstanding electrocatalytic performance should be attributed to the integration of the 3D self-supported nanostructures, the high conductivity of the framework, and particularly, the incalculable heterointerfaces formed between NiS2 and MoS2. This work provides a new strategy to study interfacial engineering and the mechanism of interface enhancement.
基金supported by the National Natural Science Foundation of China(U1705251,21871217,21573170,21433007)the National Key Research and Development Program of China(2018YFB1502001)~~
文摘Sunlight-driven photocatalytic water-splitting for hydrogen(H2)evolution is a desirable strategy to utilize solar energy.However,this strategy is restricted by insufficient light harvesting and high photogenerated electron-hole recombination rates of TiO2-based photocatalysts.Here,a graphene-modified WO3/TiO2 step-scheme heterojunction(S-scheme heterojunction)composite photocatalyst was fabricated by a facile one-step hydrothermal method.In the ternary composite,TiO2 and WO3 nanoparticles adhered closely to reduced graphene oxide(rGO)and formed a novel S-scheme heterojunction.Moreover,rGO in the composite not only supplied abundant adsorption and catalytically active sites as an ideal support but also promoted electron separation and transfer from the conduction band of TiO2 by forming a Schottky junction between TiO2 and rGO.The positive cooperative effect of the S-scheme heterojunction formed between WO3 and TiO2 and the Schottky heterojunction formed between TiO2 and graphene sheets suppressed the recombination of relatively useful electrons and holes.This effect also enhanced the light harvesting and promoted the reduction reaction at the active sites.Thus,the novel ternary WO3/TiO2/rGO composite demonstrated a remarkably enhanced photocatalytic H2 evolution rate of 245.8μmol g^-1 h^-1,which was approximately 3.5-fold that of pure TiO2.This work not only presents a low-cost graphene-based S-scheme heterojunction photocatalyst that was obtained via a feasible one-step hydrothermal approach to realize highly efficient H2 generation without using noble metals,but also provides new insights into the design of novel heterojunction photocatalysts.
文摘A lab-scale expanded granular sludge bed (EGSB) reactor was employed to evaluate the feasibility of the hydrogen energy recovery potential from high strength organic wastewater. The results showed that a maximum hydrogen production rate of 7.43 m^3 H2/m^3 reactor · d and an average hydrogen production rate of 6.44- ms H^2/ms reactor · d were achieved with the hydrogen content of 50% -56% in the biogas during the 90-day operation. At the acidogenic phase, COD removal rate was stable at about 15%. In the steady operation period, the main liquid end products were ethanol and acetic acid, which represented ethanol type fermentation. Among the liquid end products, the concentration percentage of ethanol and acetic acid amounted to 69.5% - 89. 8% and the concentration percentage of ethanol took prominent about 51.7% - 59. 1%, which is better than the utilization of substrate for the methanogenic bacteria. An ethanol type fermentation pathway was suggested in the operation of enlarged industrial continuous hydrogen bio-producing reactors.