A cost-effective,facile solution-based hot-injection synthetic route has been developed to synthesize NiSb nanoparticles in oleylamine(OAm)using commercially available inexpensive precursor with reducing toxicity at a...A cost-effective,facile solution-based hot-injection synthetic route has been developed to synthesize NiSb nanoparticles in oleylamine(OAm)using commercially available inexpensive precursor with reducing toxicity at a relatively low temperature of 160℃.Especially,an organic reductant of borane-tert-butylamine complex is intentionally involved in the reaction system to promote a fast reduction of metallic Ni and Sb for the formation of the NiSb nanoparticles.Structural characterizations reveal that the NiSb nanoparticles are hexagonal phase with space group P63/mmc and they are composed of small granules with size about 10 nm that tend to form agglomerates with porous-like geometries.This is the first report on the generation of transition metal antimonide via solution-based strategy,and the asfabricated nanoparticles possess actively electrocatalytic hydrogen evolution reaction(HER)property in acidic electrolytes when the long-chain ligand of OAm adhered on the surface of the nanoparticles is exchanged by ligand-removal and exchange procedure.It is found that the NiSb nanoparticles as a new kind of non-noble-metal HER electrocatalysts only require overpotentials of 437 and 531 mV to achieve high current densities of 10 and 50 mA/cm^2 respectively,as well as exhibit low charge transfer resistance and excellent HER stability.展开更多
Ag3PO4 microcrystals with highly enhanced visible light photocatalytic activity are prepared by a facile and simple solid state reaction at room temperature. The composition, morphology and optical properties of the a...Ag3PO4 microcrystals with highly enhanced visible light photocatalytic activity are prepared by a facile and simple solid state reaction at room temperature. The composition, morphology and optical properties of the asprepared Ag3PO4 microcrystMs are characterized by x-ray diffraction, scanning electron microscopy and UV-vis diffuse reflectance spectra. The photocatalytie properties of Ag3PO4 are investigated by the degradation of both methylene blue and methyl orange dyes under visible light irradiation. The as-prepared Ag3PO4 microcrystals possess high photocatalytic oxygen production with the rate of 673μmolh-1g-1. Moreover, the as-prepared Ag3PO4 microcrystals show an enhanced photoelectrochemistry performance under irradiation of visible light.展开更多
Two oxo-vanadium（IV） complexes, [VO（C2O4）（2,2′-bipy）（H2O）]·C2H5OH（1） and VO（C2O4）（phen）（H2O） （2）, where 2,2′-bipy=2,2′-bipyridyl, phen=1,10-phenanthroline, were synthesized as potential funct...Two oxo-vanadium（IV） complexes, [VO（C2O4）（2,2′-bipy）（H2O）]·C2H5OH（1） and VO（C2O4）（phen）（H2O） （2）, where 2,2′-bipy=2,2′-bipyridyl, phen=1,10-phenanthroline, were synthesized as potential functional models of vanadium haloperoxidases（VHPOs） in mixed solvent of ethanol and water at room temperature. The complexes were characterized by elemental analysis, infrared（IR）, UV-Vis and X-ray crystallography. Structural analyses showed that vanadium atom was coordinated by a terminal oxygen, one oxygen atom from coordinated water, two oxygen atoms from the carboxylate group of oxalic acid, and two nitrogen atoms（N1 and N2） from 2,2′-bipy/phen. Central vanadium atoms in complexes 1 and 2 were both in a distorted-octahedral environment, and some intermolecular hydrogen bonding linkages were also observed in each complex. Bromination reaction activity of the two complexes was evaluated with phenol red as organic substrate in the presence of H2O2, Br-and phosphate buffer, indicating that they can be considered as a potential functional model of VHPO. In addition, thermal analysis was also performed and discussed in detail.展开更多
Pt-based nanoframes represent a class of promising catalysts towards oxygen reduction reaction. Herein, we, for the first time, successfully prepared Pt-Pd octahedral nanoframes with ultrathin ridges less than 2 nm in...Pt-based nanoframes represent a class of promising catalysts towards oxygen reduction reaction. Herein, we, for the first time, successfully prepared Pt-Pd octahedral nanoframes with ultrathin ridges less than 2 nm in thickness. The Pt-Pd octahedral nanoframes were obtained through site-selected deposition of Pt atoms onto the edge sites of Pd octahedral seeds, followed by selective removal of the Pd octahedral cores via chemical etching. Due to that a combination of three-dimensional opens geometrical structure and Pt-skin surface compositional structure, the Pt-Pd octahedral nanoframes/C catalyst shows a mass activity of 1.15 A/mgPt towards oxygen reduction reaction, 5.8 times enhancement in mass activity relative to commercial Pt/C catalyst （0.20 A/mgPt）. Moreover, even after 8000 cycles of accelerated durability test, the Pt-Pd octahedral nanoframes/C catalyst still exhibits a mass activity which is more than three times higher than that of pristine Pt/C catalyst.展开更多
The introduction of nitrogen heteroatoms into carbon materials is a facile and efficient strategy to regulate their reactivities and facilitate their potential applications in energy conversion and storage. However,mo...The introduction of nitrogen heteroatoms into carbon materials is a facile and efficient strategy to regulate their reactivities and facilitate their potential applications in energy conversion and storage. However,most of nitrogen heteroatoms are doped into the bulk phase of carbon without site selectivity, which significantly reduces the contacts of feedstocks with the active dopants in a conductive scaffold. Herein we proposed the chemical vapor deposition of a nitrogen-doped graphene skin on the 3D porous graphene framework and donated the carbon/carbon composite as surface N-doped grapheme（SNG）. In contrast with routine N-doped graphene framework（NGF） with bulk distribution of N heteroatoms, the SNG renders a high surface N content of 1.81 at%, enhanced electrical conductivity of 31 S cm^（-1）, a large surface area of 1531 m^2 g^（-1）, a low defect density with a low I_D/I_G ratio of 1.55 calculated from Raman spectrum, and a high oxidation peak of 532.7 ℃ in oxygen atmosphere. The selective distribution of N heteroatoms on the surface of SNG affords the effective exposure of active sites at the interfaces of the electrode/electrolyte, so that more N heteroatoms are able to contact with oxygen feedstocks in oxygen reduction reaction or serve as polysulfide anchoring sites to retard the shuttle of polysulfides in a lithium–sulfur battery. This work opens a fresh viewpoint on the manipulation of active site distribution in a conductive scaffolds for multi-electron redox reaction based energy conversion and storage.展开更多
The performance of the two newly developed bimetallic catalysts based on the precursor, Mo/Al_2O_3, was compared for reverse water gas shift(RWGS) reaction. The structures of the precursor and the catalysts were studi...The performance of the two newly developed bimetallic catalysts based on the precursor, Mo/Al_2O_3, was compared for reverse water gas shift(RWGS) reaction. The structures of the precursor and the catalysts were studied using X-ray diffraction(XRD), Brunauer–Emmett–Teller(BET) analysis, inductively coupled plasma-atomic emission spectrometry(ICP-AES), CO chemisorption, temperature programmed reduction of hydrogen(H_2-TPR) and scanning electron microscopy(SEM) techniques. The activity of Fe-Mo and Co-Mo catalysts was compared in a fixed bed reactor at different temperatures. It is shown that the Co-Mo catalyst has higher CO_2 conversion at all temperature level. The time-on-stream(TOS) analysis of the activity of catalysts for the RWGS reaction was carried out over a continuous period of 60h for both catalysts. The Fe-Mo/Al_2O_3 catalyst exhibits good stability within a period of 60h, however, the Co-Mo/Al_2O_3 is gradually deactivated after 50h of reaction time. Existence of(Fe_2(MoO4_))_3 phase in Fe-Mo/Al_2O_3 catalyst makes this catalyst more stable for RWGS reaction.展开更多
The 1.3-dipolar cycloaddition reaction of 2-trifluoromethyl- oxazolone and the activated carbon-carbon multiple bond was studied and gave a convenient way to synthesize 2-trifluoromethylpyrrole derivatives.
Mono-substituted heterocyclic ketene aminals are formed by the reaction of 1-methyl-2-methylthio-imidazoline with active methylene compounds containinq an acetyl or benzoyl group by the elimination of both a methylthi...Mono-substituted heterocyclic ketene aminals are formed by the reaction of 1-methyl-2-methylthio-imidazoline with active methylene compounds containinq an acetyl or benzoyl group by the elimination of both a methylthio and an acyl group.This is resulted by the secondary reactio of the produced methanethiol to attack the more active carbonyl group.展开更多
Oxygen evolution reaction（OER） is one of the most important reactions in the energy storage devices such as metal–air batteries and unitized regenerative fuel cells（URFCs）. However, the kinetically sluggishness o...Oxygen evolution reaction（OER） is one of the most important reactions in the energy storage devices such as metal–air batteries and unitized regenerative fuel cells（URFCs）. However, the kinetically sluggishness of OER and the high prices as well as the scarcity of the most active precious metal electrocatalysts are the major bottleneck in these devices. Developing low-cost non-precious metal catalysts with high activity and stability for OER is highly desirable. A facile, in situ template method combining the dodecyl benzene sulfuric acid sodium（SDBS） assisted hydrothermal process with subsequent high-temperature treatment was developed to prepare porous Co3O4 with improved surface area and hierarchical porous structure as precious catalysts alternative for oxygen evolution reaction（OER）. Due to the unique structure, the as-prepared catalyst shows higher electrocatalytic activity than Co3O4 prepared by traditional thermal-decomposition method（noted as Co3O4-T） and commercial IrO2 catalyst for OER in 0.1M KOH aqueous solution. Moreover, it displays improved stability than Co3O4-T. The results demonstrate a highly efficient, scalable, and low cost method for developing highly active and stable OER electrocatalysts in alkaline solutions.展开更多
The development of low-cost,stable,and robust non-noble metal catalysts for water oxidation is a pivotal challenge for sustainable hydrogen production through electrocatalytic water splitting.Currently,such catalysts ...The development of low-cost,stable,and robust non-noble metal catalysts for water oxidation is a pivotal challenge for sustainable hydrogen production through electrocatalytic water splitting.Currently,such catalysts suffer from high overpotential and sluggish kinetics in oxygen evolution reactions(OERs).Herein,we report a“continuous”single-crystal honeycomb-like MXene/NiFeP_(x)–N-doped carbon(NC)heterostructure,in which ultrasmall NiFeP_(x)nanoparticles(NPs)encapsulated in the NC are tightly anchored on a layered MXene.Interestingly,this MXene/NiFeP_(x)–NC delivers outstanding OER catalytic performance,which stems from“continuous”single-crystal characteristics,abundant active sites derived from the ultrasmall NiFeP_(x)NPs,and the stable honeycomb-like heterostructure with an open structure.The experimental results are rationalized theoretically(by density functional theory(DFT)calculations),which suggests that it is the unique MXene/NiFeP_(x)–NC heterostructure that promotes the sluggish OER,thereby enabling superior durability and excellent activity with an ultralow overpotential of 240 mV at a current density of 10 mA×cm^(−2).展开更多
In order to uncover the intrinsic reasons for spontaneous combustion of sulfide minerals,representative samples were collected from typical metal mines to carry out the mechanical activation experiment.The structures ...In order to uncover the intrinsic reasons for spontaneous combustion of sulfide minerals,representative samples were collected from typical metal mines to carry out the mechanical activation experiment.The structures and heat behaviors of activated samples were characterized by scanning electron microscopy（SEM）,X-ray diffraction（XRD） analysis,and simultaneous thermal analysis（STA）.It is found that the sulfide minerals after mechanical activation show many changes with increased specific surface areas,aggregation phenomenon,decreased diffraction peak intensity,broadened diffraction peak,declined initial temperatures of heat release and self-ignition points.A new theory for explaining the spontaneous combustion of sulfide minerals is put forward：the chemical reaction activity of sulfide minerals is heightened by all kinds of mechanical forces during the mining,and the spontaneous combustion takes place finally under proper environment.展开更多
MgH_(2),TiH_(2),and ZrH_(2) are three typical metal hydrides that have been gradually applied to composite explosives and propellants as additives in recent years.To evaluate ignition sensitivity and explosion severit...MgH_(2),TiH_(2),and ZrH_(2) are three typical metal hydrides that have been gradually applied to composite explosives and propellants as additives in recent years.To evaluate ignition sensitivity and explosion severity,the Hartmann device and spherical pressure vessel were used to test ignition energy and explosion pressure,respectively.The results showed that the ignition sensitivity of ZrH_(2),TiH_(2) and MgH_(2) gradually increased.When the concentration of MgH_(2) is 83.0 g/m^(3) in Hartmann device,the ignition energy attained a minimum of 10.0 mJ.The explosion pressure of MgH_(2) were 1.44 times and 1.76 times that of TiH_(2) and ZrH_(2),respectively,and the explosion pressure rising rate were 3.97 times and 9.96 times that of TiH_(2) and ZrH_(2),respectively,through the spherical pressure vessel.It indicated that the reaction reactivity and reaction rate of MgH_(2) were higher than that of TiH_(2) and ZrH_(2).In addition,to conduct in edepth theoretical analysis of ignition sensitivity and explosion severity,gas production and combustion heat per unit mass of ZrH_(2),TiH_(2) and MgH_(2) were tested by mercury manometer and oxygen bomb calorimetry.The experimental results revealed that MgH_(2) had a relatively high gas production per unit mass(5.15 mL/g),while TiH_(2) and ZrH_(2) both had a gas production of less than 2.0 mL/g.Their thermal stability gradually increased,leading to a gradual increase in ignition energy.Furthermore,compared with theoretical combustion heat,the combustion ratio of MgH_(2),TiH_(2) and ZrH_(2) was more than 96.0%,with combustion heat value of 29.96,20.94 and 12.22 MJ/kg,respectively,which was consistent with the explosion pressure and explosion severity test results.展开更多
Sustainable conversion of carbon dioxide(CO_(2))to high value-added chemicals and fuels is a promising solution to solve the problem of excessive CO_(2) emissions and alleviate the shortage of fossil fuels,maintaining...Sustainable conversion of carbon dioxide(CO_(2))to high value-added chemicals and fuels is a promising solution to solve the problem of excessive CO_(2) emissions and alleviate the shortage of fossil fuels,maintaining the balance of the carbon cycle in nature.The development of catalytic system is of great significance to improve the efficiency and selectivity for electrochemical CO_(2) conversion.In particular,bismuth(Bi)based catalysts are the most promising candidates,while confronting challenges.This review aims to elucidate the fundamental issues of efficient and stable Bi-based catalysts,constructing a bridge between the category,synthesis approach and electrochemical performance.In this review,the categories of Bi-based catalysts are firstly introduced,such as metals,alloys,single atoms,compounds and composites.Followed by the statement of the reliable and versatile synthetic approaches,the representative optimization strategies,such as morphology manipulation,defect engineering,component and heterostructure regulation,have been highlighted in the discussion,paving in-depth insight upon the design principles,reaction activity,selectivity and stability.Afterward,in situ characterization techniques will be discussed to illustrate the mechanisms of electrochemical CO_(2) conversion.In the end,the challenges and perspectives are also provided,promoting a systematic understanding in terms of the bottleneck and opportunities in the field of electrochemical CO_(2) conversion.展开更多
Ce x Ti 1- x O 2 mixed oxides of different mole ratios ( x =0, 0.1, 0.2～0.9, 1.0) were prepared by co precipitation of TiCl 4 with Ce(NO 3) 3 and then loaded with different amounts of CuO. The effe...Ce x Ti 1- x O 2 mixed oxides of different mole ratios ( x =0, 0.1, 0.2～0.9, 1.0) were prepared by co precipitation of TiCl 4 with Ce(NO 3) 3 and then loaded with different amounts of CuO. The effects of CuO on NO+CO reaction were investigated, and the structure and reductive properties of various CuO/Ce x Ti 1- x O 2 were characterized by the methodologies of BET, TPR and XRD. The results show that different Ce/Ti mole ratios and calcination temperatures induce changes of structure and reductive properties of the Ce x Ti 1- x O 2 mixed oxides. When x =0.1～0.5, amorphous CeTi 2O 6 phase mainly forms at 650 ℃ compared to the formation of CeTi 2O 6 which crystallizes at 800 ℃. When x >0.6, some TiO 2 enters the CeO 2 lattice and a CeO 2 TiO 2 solid solution is formed. The activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 650 ℃ is largely affected by the x values, which is the highest when x =0.3, 0.4 and 0.9. The NO conversion reaches 70% at a reaction temperature of 150 ℃. By comparison, the x values have little effect on the activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 800 ℃ . There are strong interactions between CuO and CeTi 2O 6, i.e., formation of the CeTi 2O 6 phase shifts the CuO reduction peak temperature from 380 to 200 ℃, and CuO, in turn, shifts the CeTi 2O 6 reduction peak temperature from 600 to 300 ℃.展开更多
Digestion behaviors of several single silicon-containing minerals including kaolinite, illite and pyrophyllite in aluminate solution were investigated. The result shows that the digestion rates of kaolinite, illite an...Digestion behaviors of several single silicon-containing minerals including kaolinite, illite and pyrophyllite in aluminate solution were investigated. The result shows that the digestion rates of kaolinite, illite and pyrophyllite in aluminate solution were influenced by reaction conditions such as temperature. Adopting quantum chemistry theoretical calculation, using CASTEM procedure module, the slab model of kaolinite, illite, pyrophyllite and their ordinary complete cleavage plane (001) were geometry optimized at GGA-PW91 level. The micro-essence of the different reaction activities among kaolinite, illite, pyrophyllite in aluminate solution was opened out. It is found that the reaction activities of kaolinite, illite, pyrophyllite are obviously different and the reaction activity of pyrophyllite is the highest. The Si—O bond strength of illite is the strongest and its Al—O bond strength is comparatively the weakest, so Si in it is the most difficult to be removed. The Si—O bond strength of pyrophyllite is the weakest, so Si in it is relatively easy to be removed. The micro-electron structure of complete cleavage plane and the Si—O bond strength of kaolinite, illite and pyrophyllite are evidently influenced by the existence of OH-, of which the surface character and the reduction of Si—O bond strength of kaolinite are influenced most greatly by OH-. Therefore, the desilication of kaolinite in alkaline solution at relatively low temperature is easier.展开更多
Amorphous alloy(MGs)is a solid alloy with disordered atomic accumulation obtained by ultra-rapid solidification of alloy melt.The atom deviates from the equilibrium position and is in metastable state.Up to now,a larg...Amorphous alloy(MGs)is a solid alloy with disordered atomic accumulation obtained by ultra-rapid solidification of alloy melt.The atom deviates from the equilibrium position and is in metastable state.Up to now,a large number of MGs have been applied to the treatment of dye and heavy metal contaminated wastewater and ideal experimental results have been obtained.However,there is no literature to systematically summarize the chemical reaction and degradation mechanism in the process of degradation.On the basis of reviewing the classification,application,and synthesis of MGs,this paper introduces in detail the chemical reactions such as decolorization,mineralization,and ion leaching of Fe-based amorphous alloy(Fe-MGs)in the degradation of organic and inorganic salt wastewater through direct reduction or advanced oxidation mechanism.Compared with crystalline materials,the higher reaction rate of Fe-MGs can be attributed to lower activation energy,negative redox potential,loose product layer,and band structure with downward shift of valence band top.Finally,some suggestions and prospects are put forward for the limitations and research prospects of MGs in the environmental field,which provides a new idea for the synthesis of new environmental functional materials.展开更多
We propose a catalytically activated duplication model to mimic the coagulation and duplication of the DNA polymer system under the catalysis of the primer RNA. In the model, two aggregates of the same species can coa...We propose a catalytically activated duplication model to mimic the coagulation and duplication of the DNA polymer system under the catalysis of the primer RNA. In the model, two aggregates of the same species can coagulate themselves and a DNA aggregate of any size can yield a new monomer or double itself with the help of RNA aggregates. By employing the mean-field rate equation approach we analytically investigate the evolution behaviour of the system. For the system with catalysis-driven monomer duplications, the aggregate size distribution of DNA polymers αk（t） always follows a power law in size in the long-time limit, and it decreases with time or approaches a time-independent steady-state form in the case of the duplication rate independent of the size of the mother aggregates, while it increases with time increasing in the case of the duplication rate proportional to the size of the mother aggregates. For the system with complete catalysis-driven duplications, the aggregate size distribution αk（t） approaches a generalized or modified scaling form.展开更多
We propose a catalytically activated replication-decline model of three species, in which two aggregates of the same species can coagulate themselves, an A aggregate of any size can replicate itself with the help of B...We propose a catalytically activated replication-decline model of three species, in which two aggregates of the same species can coagulate themselves, an A aggregate of any size can replicate itself with the help of B aggregates, and the decline of A aggregate occurs under the catalysis of C aggregates. By means of mean-field rate equations, we derive the asymptotic solutions of the aggregate size distribution ak（t） of species A, which is found to depend strongly on the competition among three mechanisms： the self-coagulation of species A, the replication of species A catalyzed by species B, and the decline of species A catalyzed by species C. When the self-coagulation of species A dominates the system, the aggregate size distribution a^（t） satisfies the conventional scaling form. When the catalyzed replication process dominates the system, ak（t） takes the generalized scaling form. When the catalyzed decline process dominates the system, ak（t） approaches the modified scaling form.展开更多
We propose a catalytically activated aggregation-fragmentation model of three species, in which two clusters of species A can coagulate into a larger one under the catalysis of B clusters; otherwise, one cluster of sp...We propose a catalytically activated aggregation-fragmentation model of three species, in which two clusters of species A can coagulate into a larger one under the catalysis of B clusters; otherwise, one cluster of species A will fragment into two smaller clusters under the catalysis of C clusters. By means of mean-field rate equations, we derive the asymptotic solutions of the cluster-mass distributions ak（t） of species A, which is found to depend strongly on the competition between the catalyzed aggregation process and the catalyzed fragmentation process. When the catalyzed aggregation process dominates the system, the cluster-mass distribution ak（t） satisfies the conventional scaling form. When the catalyzed fragmentation process dominates the system, the scaling description of ak （t） breaks down completely and the monodisperse initial condition of species A would not be changed in the long-time limit. In the marginal case when the effects of catalyzed aggregation and catalyzed fragmentation counteract each other, ak（t） takes the modified scaling form and the system can eventually evolve to a steady state.展开更多
基金supported by the National Natural Science Foundation of China(No.21571166 and No.51271173)
文摘A cost-effective,facile solution-based hot-injection synthetic route has been developed to synthesize NiSb nanoparticles in oleylamine(OAm)using commercially available inexpensive precursor with reducing toxicity at a relatively low temperature of 160℃.Especially,an organic reductant of borane-tert-butylamine complex is intentionally involved in the reaction system to promote a fast reduction of metallic Ni and Sb for the formation of the NiSb nanoparticles.Structural characterizations reveal that the NiSb nanoparticles are hexagonal phase with space group P63/mmc and they are composed of small granules with size about 10 nm that tend to form agglomerates with porous-like geometries.This is the first report on the generation of transition metal antimonide via solution-based strategy,and the asfabricated nanoparticles possess actively electrocatalytic hydrogen evolution reaction(HER)property in acidic electrolytes when the long-chain ligand of OAm adhered on the surface of the nanoparticles is exchanged by ligand-removal and exchange procedure.It is found that the NiSb nanoparticles as a new kind of non-noble-metal HER electrocatalysts only require overpotentials of 437 and 531 mV to achieve high current densities of 10 and 50 mA/cm^2 respectively,as well as exhibit low charge transfer resistance and excellent HER stability.
基金Supported by the Beijing Higher Education Young Elite Teacher Project under Grant No YETP1297the Fundamental Research Funds for the Central Universities under Grant No 2014MDLXYZY05+1 种基金the Undergraduate Innovative Test Program of China under Grant Nos GCCX2015110009 and BEIJ2015110024the National Natural Science Foundation of China under Grant Nos11074312 and 11374377
文摘Ag3PO4 microcrystals with highly enhanced visible light photocatalytic activity are prepared by a facile and simple solid state reaction at room temperature. The composition, morphology and optical properties of the asprepared Ag3PO4 microcrystMs are characterized by x-ray diffraction, scanning electron microscopy and UV-vis diffuse reflectance spectra. The photocatalytie properties of Ag3PO4 are investigated by the degradation of both methylene blue and methyl orange dyes under visible light irradiation. The as-prepared Ag3PO4 microcrystals possess high photocatalytic oxygen production with the rate of 673μmolh-1g-1. Moreover, the as-prepared Ag3PO4 microcrystals show an enhanced photoelectrochemistry performance under irradiation of visible light.
基金Supported by the National Natural Science Foundation of China(No.21071071)the Education Foundation of Dalian City in China(No.2009J21DW004)
文摘Two oxo-vanadium（IV） complexes, [VO（C2O4）（2,2′-bipy）（H2O）]·C2H5OH（1） and VO（C2O4）（phen）（H2O） （2）, where 2,2′-bipy=2,2′-bipyridyl, phen=1,10-phenanthroline, were synthesized as potential functional models of vanadium haloperoxidases（VHPOs） in mixed solvent of ethanol and water at room temperature. The complexes were characterized by elemental analysis, infrared（IR）, UV-Vis and X-ray crystallography. Structural analyses showed that vanadium atom was coordinated by a terminal oxygen, one oxygen atom from coordinated water, two oxygen atoms from the carboxylate group of oxalic acid, and two nitrogen atoms（N1 and N2） from 2,2′-bipy/phen. Central vanadium atoms in complexes 1 and 2 were both in a distorted-octahedral environment, and some intermolecular hydrogen bonding linkages were also observed in each complex. Bromination reaction activity of the two complexes was evaluated with phenol red as organic substrate in the presence of H2O2, Br-and phosphate buffer, indicating that they can be considered as a potential functional model of VHPO. In addition, thermal analysis was also performed and discussed in detail.
基金This work is supported by Collaborative Innovation Center of Suzhou Nano Science and Technology, Ministry of Science and Technology of China （No.2014CB932700）, the National Natural Science Foundation of China （No.21603208, No.21573206, and No.51371164）, the China Postdoctoral Science Foundation （No.2015M580536, No.2016T90569）, Key Research Program of Frontier Sciences, CAS （QYZDBSSW- SLH017）, Strategic Priority Research Program B of the CAS （No.XDB01020000）, Hefei Science Center, CAS （No.2015HSC-UP016）, and Fundamental Research Funds for the Central Universities.
文摘Pt-based nanoframes represent a class of promising catalysts towards oxygen reduction reaction. Herein, we, for the first time, successfully prepared Pt-Pd octahedral nanoframes with ultrathin ridges less than 2 nm in thickness. The Pt-Pd octahedral nanoframes were obtained through site-selected deposition of Pt atoms onto the edge sites of Pd octahedral seeds, followed by selective removal of the Pd octahedral cores via chemical etching. Due to that a combination of three-dimensional opens geometrical structure and Pt-skin surface compositional structure, the Pt-Pd octahedral nanoframes/C catalyst shows a mass activity of 1.15 A/mgPt towards oxygen reduction reaction, 5.8 times enhancement in mass activity relative to commercial Pt/C catalyst （0.20 A/mgPt）. Moreover, even after 8000 cycles of accelerated durability test, the Pt-Pd octahedral nanoframes/C catalyst still exhibits a mass activity which is more than three times higher than that of pristine Pt/C catalyst.
基金supported by the National Key Research and Development Program(2016YFA0202500 and 2016YFA0200102)the Natural Scientific Foundation of China(21776019)
文摘The introduction of nitrogen heteroatoms into carbon materials is a facile and efficient strategy to regulate their reactivities and facilitate their potential applications in energy conversion and storage. However,most of nitrogen heteroatoms are doped into the bulk phase of carbon without site selectivity, which significantly reduces the contacts of feedstocks with the active dopants in a conductive scaffold. Herein we proposed the chemical vapor deposition of a nitrogen-doped graphene skin on the 3D porous graphene framework and donated the carbon/carbon composite as surface N-doped grapheme（SNG）. In contrast with routine N-doped graphene framework（NGF） with bulk distribution of N heteroatoms, the SNG renders a high surface N content of 1.81 at%, enhanced electrical conductivity of 31 S cm^（-1）, a large surface area of 1531 m^2 g^（-1）, a low defect density with a low I_D/I_G ratio of 1.55 calculated from Raman spectrum, and a high oxidation peak of 532.7 ℃ in oxygen atmosphere. The selective distribution of N heteroatoms on the surface of SNG affords the effective exposure of active sites at the interfaces of the electrode/electrolyte, so that more N heteroatoms are able to contact with oxygen feedstocks in oxygen reduction reaction or serve as polysulfide anchoring sites to retard the shuttle of polysulfides in a lithium–sulfur battery. This work opens a fresh viewpoint on the manipulation of active site distribution in a conductive scaffolds for multi-electron redox reaction based energy conversion and storage.
基金the Iranian Nano Technology Initiative Council and the Petroleum University of Technology for financial support
文摘The performance of the two newly developed bimetallic catalysts based on the precursor, Mo/Al_2O_3, was compared for reverse water gas shift(RWGS) reaction. The structures of the precursor and the catalysts were studied using X-ray diffraction(XRD), Brunauer–Emmett–Teller(BET) analysis, inductively coupled plasma-atomic emission spectrometry(ICP-AES), CO chemisorption, temperature programmed reduction of hydrogen(H_2-TPR) and scanning electron microscopy(SEM) techniques. The activity of Fe-Mo and Co-Mo catalysts was compared in a fixed bed reactor at different temperatures. It is shown that the Co-Mo catalyst has higher CO_2 conversion at all temperature level. The time-on-stream(TOS) analysis of the activity of catalysts for the RWGS reaction was carried out over a continuous period of 60h for both catalysts. The Fe-Mo/Al_2O_3 catalyst exhibits good stability within a period of 60h, however, the Co-Mo/Al_2O_3 is gradually deactivated after 50h of reaction time. Existence of(Fe_2(MoO4_))_3 phase in Fe-Mo/Al_2O_3 catalyst makes this catalyst more stable for RWGS reaction.
文摘The 1.3-dipolar cycloaddition reaction of 2-trifluoromethyl- oxazolone and the activated carbon-carbon multiple bond was studied and gave a convenient way to synthesize 2-trifluoromethylpyrrole derivatives.
文摘Mono-substituted heterocyclic ketene aminals are formed by the reaction of 1-methyl-2-methylthio-imidazoline with active methylene compounds containinq an acetyl or benzoyl group by the elimination of both a methylthio and an acyl group.This is resulted by the secondary reactio of the produced methanethiol to attack the more active carbonyl group.
基金supported by the Youth Innovation Promotion Association(no.2015147)CAS and National Program on Key Basic Research Project(973 Program,2012CB215500)+1 种基金the Outstanding Youngest Scientist FoundationChinese Academy of Sciences(CAS)
文摘Oxygen evolution reaction（OER） is one of the most important reactions in the energy storage devices such as metal–air batteries and unitized regenerative fuel cells（URFCs）. However, the kinetically sluggishness of OER and the high prices as well as the scarcity of the most active precious metal electrocatalysts are the major bottleneck in these devices. Developing low-cost non-precious metal catalysts with high activity and stability for OER is highly desirable. A facile, in situ template method combining the dodecyl benzene sulfuric acid sodium（SDBS） assisted hydrothermal process with subsequent high-temperature treatment was developed to prepare porous Co3O4 with improved surface area and hierarchical porous structure as precious catalysts alternative for oxygen evolution reaction（OER）. Due to the unique structure, the as-prepared catalyst shows higher electrocatalytic activity than Co3O4 prepared by traditional thermal-decomposition method（noted as Co3O4-T） and commercial IrO2 catalyst for OER in 0.1M KOH aqueous solution. Moreover, it displays improved stability than Co3O4-T. The results demonstrate a highly efficient, scalable, and low cost method for developing highly active and stable OER electrocatalysts in alkaline solutions.
基金supported by the National Natural Science Foundation of China(No.22269010)the Training Program for Academic and Technical Leaders of Major Disciplines in Jiangxi Province(No.20212BCJ23020)+1 种基金the Science and Technology Project of Jiangxi Provincial Department of Education(No.GJJ211305)Jingdezhen Science and Technology Planning Project(No.20212GYZD009-04)。
文摘The development of low-cost,stable,and robust non-noble metal catalysts for water oxidation is a pivotal challenge for sustainable hydrogen production through electrocatalytic water splitting.Currently,such catalysts suffer from high overpotential and sluggish kinetics in oxygen evolution reactions(OERs).Herein,we report a“continuous”single-crystal honeycomb-like MXene/NiFeP_(x)–N-doped carbon(NC)heterostructure,in which ultrasmall NiFeP_(x)nanoparticles(NPs)encapsulated in the NC are tightly anchored on a layered MXene.Interestingly,this MXene/NiFeP_(x)–NC delivers outstanding OER catalytic performance,which stems from“continuous”single-crystal characteristics,abundant active sites derived from the ultrasmall NiFeP_(x)NPs,and the stable honeycomb-like heterostructure with an open structure.The experimental results are rationalized theoretically(by density functional theory(DFT)calculations),which suggests that it is the unique MXene/NiFeP_(x)–NC heterostructure that promotes the sluggish OER,thereby enabling superior durability and excellent activity with an ultralow overpotential of 240 mV at a current density of 10 mA×cm^(−2).
基金Project(2012J05088) supported by the Natural Science Foundation of Fujian Province,ChinaProject(022409) supported by the School Talent Foundation of Fuzhou University,China
文摘In order to uncover the intrinsic reasons for spontaneous combustion of sulfide minerals,representative samples were collected from typical metal mines to carry out the mechanical activation experiment.The structures and heat behaviors of activated samples were characterized by scanning electron microscopy（SEM）,X-ray diffraction（XRD） analysis,and simultaneous thermal analysis（STA）.It is found that the sulfide minerals after mechanical activation show many changes with increased specific surface areas,aggregation phenomenon,decreased diffraction peak intensity,broadened diffraction peak,declined initial temperatures of heat release and self-ignition points.A new theory for explaining the spontaneous combustion of sulfide minerals is put forward：the chemical reaction activity of sulfide minerals is heightened by all kinds of mechanical forces during the mining,and the spontaneous combustion takes place finally under proper environment.
基金This work was greatly supported by the Natural Science Foundation of China(11802272)the Open Research Fund Program of Science and Technology on Aerospace Chemical Power Laboratory(STACPL220181B01).
文摘MgH_(2),TiH_(2),and ZrH_(2) are three typical metal hydrides that have been gradually applied to composite explosives and propellants as additives in recent years.To evaluate ignition sensitivity and explosion severity,the Hartmann device and spherical pressure vessel were used to test ignition energy and explosion pressure,respectively.The results showed that the ignition sensitivity of ZrH_(2),TiH_(2) and MgH_(2) gradually increased.When the concentration of MgH_(2) is 83.0 g/m^(3) in Hartmann device,the ignition energy attained a minimum of 10.0 mJ.The explosion pressure of MgH_(2) were 1.44 times and 1.76 times that of TiH_(2) and ZrH_(2),respectively,and the explosion pressure rising rate were 3.97 times and 9.96 times that of TiH_(2) and ZrH_(2),respectively,through the spherical pressure vessel.It indicated that the reaction reactivity and reaction rate of MgH_(2) were higher than that of TiH_(2) and ZrH_(2).In addition,to conduct in edepth theoretical analysis of ignition sensitivity and explosion severity,gas production and combustion heat per unit mass of ZrH_(2),TiH_(2) and MgH_(2) were tested by mercury manometer and oxygen bomb calorimetry.The experimental results revealed that MgH_(2) had a relatively high gas production per unit mass(5.15 mL/g),while TiH_(2) and ZrH_(2) both had a gas production of less than 2.0 mL/g.Their thermal stability gradually increased,leading to a gradual increase in ignition energy.Furthermore,compared with theoretical combustion heat,the combustion ratio of MgH_(2),TiH_(2) and ZrH_(2) was more than 96.0%,with combustion heat value of 29.96,20.94 and 12.22 MJ/kg,respectively,which was consistent with the explosion pressure and explosion severity test results.
文摘Sustainable conversion of carbon dioxide(CO_(2))to high value-added chemicals and fuels is a promising solution to solve the problem of excessive CO_(2) emissions and alleviate the shortage of fossil fuels,maintaining the balance of the carbon cycle in nature.The development of catalytic system is of great significance to improve the efficiency and selectivity for electrochemical CO_(2) conversion.In particular,bismuth(Bi)based catalysts are the most promising candidates,while confronting challenges.This review aims to elucidate the fundamental issues of efficient and stable Bi-based catalysts,constructing a bridge between the category,synthesis approach and electrochemical performance.In this review,the categories of Bi-based catalysts are firstly introduced,such as metals,alloys,single atoms,compounds and composites.Followed by the statement of the reliable and versatile synthetic approaches,the representative optimization strategies,such as morphology manipulation,defect engineering,component and heterostructure regulation,have been highlighted in the discussion,paving in-depth insight upon the design principles,reaction activity,selectivity and stability.Afterward,in situ characterization techniques will be discussed to illustrate the mechanisms of electrochemical CO_(2) conversion.In the end,the challenges and perspectives are also provided,promoting a systematic understanding in terms of the bottleneck and opportunities in the field of electrochemical CO_(2) conversion.
文摘Ce x Ti 1- x O 2 mixed oxides of different mole ratios ( x =0, 0.1, 0.2～0.9, 1.0) were prepared by co precipitation of TiCl 4 with Ce(NO 3) 3 and then loaded with different amounts of CuO. The effects of CuO on NO+CO reaction were investigated, and the structure and reductive properties of various CuO/Ce x Ti 1- x O 2 were characterized by the methodologies of BET, TPR and XRD. The results show that different Ce/Ti mole ratios and calcination temperatures induce changes of structure and reductive properties of the Ce x Ti 1- x O 2 mixed oxides. When x =0.1～0.5, amorphous CeTi 2O 6 phase mainly forms at 650 ℃ compared to the formation of CeTi 2O 6 which crystallizes at 800 ℃. When x >0.6, some TiO 2 enters the CeO 2 lattice and a CeO 2 TiO 2 solid solution is formed. The activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 650 ℃ is largely affected by the x values, which is the highest when x =0.3, 0.4 and 0.9. The NO conversion reaches 70% at a reaction temperature of 150 ℃. By comparison, the x values have little effect on the activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 800 ℃ . There are strong interactions between CuO and CeTi 2O 6, i.e., formation of the CeTi 2O 6 phase shifts the CuO reduction peak temperature from 380 to 200 ℃, and CuO, in turn, shifts the CeTi 2O 6 reduction peak temperature from 600 to 300 ℃.
基金Project(2005CB623702) supported by the National Basic Research Program of China
文摘Digestion behaviors of several single silicon-containing minerals including kaolinite, illite and pyrophyllite in aluminate solution were investigated. The result shows that the digestion rates of kaolinite, illite and pyrophyllite in aluminate solution were influenced by reaction conditions such as temperature. Adopting quantum chemistry theoretical calculation, using CASTEM procedure module, the slab model of kaolinite, illite, pyrophyllite and their ordinary complete cleavage plane (001) were geometry optimized at GGA-PW91 level. The micro-essence of the different reaction activities among kaolinite, illite, pyrophyllite in aluminate solution was opened out. It is found that the reaction activities of kaolinite, illite, pyrophyllite are obviously different and the reaction activity of pyrophyllite is the highest. The Si—O bond strength of illite is the strongest and its Al—O bond strength is comparatively the weakest, so Si in it is the most difficult to be removed. The Si—O bond strength of pyrophyllite is the weakest, so Si in it is relatively easy to be removed. The micro-electron structure of complete cleavage plane and the Si—O bond strength of kaolinite, illite and pyrophyllite are evidently influenced by the existence of OH-, of which the surface character and the reduction of Si—O bond strength of kaolinite are influenced most greatly by OH-. Therefore, the desilication of kaolinite in alkaline solution at relatively low temperature is easier.
基金This research was funded by the National Natural Science Foundation of China(NSFC)[Grant Nos.51661015 and 52061024]the Natural Science Foundation of Zhejiang Province[Grant No.LQ20E010002].
文摘Amorphous alloy(MGs)is a solid alloy with disordered atomic accumulation obtained by ultra-rapid solidification of alloy melt.The atom deviates from the equilibrium position and is in metastable state.Up to now,a large number of MGs have been applied to the treatment of dye and heavy metal contaminated wastewater and ideal experimental results have been obtained.However,there is no literature to systematically summarize the chemical reaction and degradation mechanism in the process of degradation.On the basis of reviewing the classification,application,and synthesis of MGs,this paper introduces in detail the chemical reactions such as decolorization,mineralization,and ion leaching of Fe-based amorphous alloy(Fe-MGs)in the degradation of organic and inorganic salt wastewater through direct reduction or advanced oxidation mechanism.Compared with crystalline materials,the higher reaction rate of Fe-MGs can be attributed to lower activation energy,negative redox potential,loose product layer,and band structure with downward shift of valence band top.Finally,some suggestions and prospects are put forward for the limitations and research prospects of MGs in the environmental field,which provides a new idea for the synthesis of new environmental functional materials.
基金supported by the National Natural Science Foundation of China (Grant Nos 10275048,10305009 and 10875086)by the Zhejiang Provincial Natural Science Foundation of China (Grant No 102067)
文摘We propose a catalytically activated duplication model to mimic the coagulation and duplication of the DNA polymer system under the catalysis of the primer RNA. In the model, two aggregates of the same species can coagulate themselves and a DNA aggregate of any size can yield a new monomer or double itself with the help of RNA aggregates. By employing the mean-field rate equation approach we analytically investigate the evolution behaviour of the system. For the system with catalysis-driven monomer duplications, the aggregate size distribution of DNA polymers αk（t） always follows a power law in size in the long-time limit, and it decreases with time or approaches a time-independent steady-state form in the case of the duplication rate independent of the size of the mother aggregates, while it increases with time increasing in the case of the duplication rate proportional to the size of the mother aggregates. For the system with complete catalysis-driven duplications, the aggregate size distribution αk（t） approaches a generalized or modified scaling form.
基金supported by the National Natural Science Foundation of China (Grant Nos. 10875086 and 11145004)
文摘We propose a catalytically activated replication-decline model of three species, in which two aggregates of the same species can coagulate themselves, an A aggregate of any size can replicate itself with the help of B aggregates, and the decline of A aggregate occurs under the catalysis of C aggregates. By means of mean-field rate equations, we derive the asymptotic solutions of the aggregate size distribution ak（t） of species A, which is found to depend strongly on the competition among three mechanisms： the self-coagulation of species A, the replication of species A catalyzed by species B, and the decline of species A catalyzed by species C. When the self-coagulation of species A dominates the system, the aggregate size distribution a^（t） satisfies the conventional scaling form. When the catalyzed replication process dominates the system, ak（t） takes the generalized scaling form. When the catalyzed decline process dominates the system, ak（t） approaches the modified scaling form.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.10275048 and 10875086)by the Science Foundation of Shihezi University (Grant No.RCZX200745)
文摘We propose a catalytically activated aggregation-fragmentation model of three species, in which two clusters of species A can coagulate into a larger one under the catalysis of B clusters; otherwise, one cluster of species A will fragment into two smaller clusters under the catalysis of C clusters. By means of mean-field rate equations, we derive the asymptotic solutions of the cluster-mass distributions ak（t） of species A, which is found to depend strongly on the competition between the catalyzed aggregation process and the catalyzed fragmentation process. When the catalyzed aggregation process dominates the system, the cluster-mass distribution ak（t） satisfies the conventional scaling form. When the catalyzed fragmentation process dominates the system, the scaling description of ak （t） breaks down completely and the monodisperse initial condition of species A would not be changed in the long-time limit. In the marginal case when the effects of catalyzed aggregation and catalyzed fragmentation counteract each other, ak（t） takes the modified scaling form and the system can eventually evolve to a steady state.
