PtRuIn/C electrocatalysts( 20% metal loading by weight) were prepared by sodium borohydride reduction process using H_2PtCl6·6H_2O,RuCl_3·xH_2O and InCl_3·xH_2O as metal sources,borohydride as reducing ...PtRuIn/C electrocatalysts( 20% metal loading by weight) were prepared by sodium borohydride reduction process using H_2PtCl6·6H_2O,RuCl_3·xH_2O and InCl_3·xH_2O as metal sources,borohydride as reducing agent and Carbon Vulcan XC72 as support. The synthetized PtRuIn/C electrocatalysts were characterized by X-ray diffraction( XRD),energy dispersive analysis( EDX),transmission electron microscopy( TEM),cyclic voltammetry( CV),chronoamperommetry( CA) and polarization curves in alkaline and acidic electrolytes( single cell experiments). The XRD patterns showPtpeaks are attributed to the face-centered cubic( fcc) structure,and a shift of Pt( fcc) peaks indicates that Ru or In is incorporated into Ptlattice. TEMmicrographs showmetal nanoparticles with an average nanoparticle size between 2.7 and 3.5 nm. Methanol oxidation in acidic and alkaline electrolytes was investigated at room temperature,by CV and CA. PtRu/C( 50 ∶ 50) shows the highest activity among all electrocatalysts in study considering methanol oxidation for acidic and alkaline electrolyte. Polarization curves at 80 ℃ showPtRuIn/C( 50 ∶ 25 ∶ 25)with superior performance for methanol oxidation,when compared to Pt/C,PtIn/C and PtRu/C for both electrolytes. The best performance obtained by PtRuIn/C( 50 ∶ 25 ∶ 25) in real conditions could be associated with the increased kinetics reaction and/or with the occurrence simultaneously of the bifunctional mechanism and electronic effect resulting from the presence of Ptalloy.展开更多
The main objective of this paper was to characterize the voltammetric profiles of the Pt/C,Pt/C-ATO,Pd/C and Pd/CATO electrocatalysts and study their catalytic activities for methane oxidation in an acidic electrolyte...The main objective of this paper was to characterize the voltammetric profiles of the Pt/C,Pt/C-ATO,Pd/C and Pd/CATO electrocatalysts and study their catalytic activities for methane oxidation in an acidic electrolyte at 25 ℃ and in a direct methane proton exchange membrane fuel cell at 80 ℃. The electrocatalysts prepared also were characterized by X-ray diffraction( XRD) and transmission electron microscopy( TEM). The diffractograms of the Pt/C and Pt/C-ATO electrocatalysts show four peaks associated with Pt face-centered cubic( fcc) structure,and the diffractograms of Pd/C and Pd/C-ATO show four peaks associated with Pd face-centered cubic( fcc) structure. For Pt/C-ATO and Pd/C-ATO,characteristic peaks of cassiterite( SnO_2) phase are observed,which are associated with Sb-doped SnO_2( ATO) used as supports for electrocatalysts. Cyclic voltammograms( CV) of all electrocatalysts after adsorption of methane show that there is a current increase during the anodic scan. However,this effect is more pronounced for Pt/C-ATO and Pd/C-ATO. This process is related to the oxidation of the adsorbed species through the bifunctional mechanism,where ATO provides oxygenated species for the oxidation of CO or HCO intermediates adsorbed in Pt or Pd sites. From in situ ATR-FTIR( Attenuated Total Reflectance-Fourier Transform Infrared) experiments for all electrocatalysts prepared the formation of HCO or CO intermediates are observed,which indicates the production of carbon dioxide. Polarization curves at 80 ℃in a direct methane fuel cell( DMEFC) show that Pd/C and Pt/C electroacatalysts have superior performance to Pd/C-ATO and Pt/C-ATO in methane oxidation.展开更多
Mining activities have created great wealth, but they have also discharged large quantities of tailings. As an important source of heavy metal contamination, sulfide tailings are usually disposed of in open-air impoun...Mining activities have created great wealth, but they have also discharged large quantities of tailings. As an important source of heavy metal contamination, sulfide tailings are usually disposed of in open-air impoundments and thus are exposed to microbial oxidation. Microbial activities greatly enhance sulfide oxidation and result in the release of heavy metals and the precipitation of iron (oxy) hydroxides and sulfates. These secondary minerals in turn influence the mobility of dissolved metals and play important roles in the natural attenuation of heavy metals. Elucidating the microbe–mineral interactions in tailings will improve our understanding of the environmental consequence of mining activities.展开更多
Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atm...Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.展开更多
The mineralogical features of the oxidation-reduction of graphite deposit in pingdu, Shandong province were studied by field search, polarization microscope, X-ray diffraction (XRD) and SEM. The results show that, the...The mineralogical features of the oxidation-reduction of graphite deposit in pingdu, Shandong province were studied by field search, polarization microscope, X-ray diffraction (XRD) and SEM. The results show that, the major rocks of the reduction graphite zone are graphite-quartz anorthosite, gabbro. The major rocks of the oxidation graphite zone are marble with graphite, biotite granite, monzogranite. The main minerals of the reduction zone are plagioclase, pyroxene, quartz, pyrite. The graphite is aphanitic graphite appearing as dense massive, layered, spherical aggregates. The main minerals of the oxidation zone are calcite, quartz, K-feldspar, biotite, amphibole, chlorite. The graphite is flake graphite uniformly dispersed in the loose, and strongly erosion rocks. A large number of rocks in the area have been suffered chloritization, regional metamorphism, indicating that the formation of the graphite deposit should be related with gabbro melting. The carbon source in the lower part was taken into the mine, and then experienced regional metamorphism.展开更多
Ti-6Al-4V alloy powder was prepared through a two-step reduction of a mixture of TiO_(2),V_(2)O_(5) and Al_(2)O_(3) in this study.The oxide mixture was first reduced by Mg in MgCl_(2) at 750℃ in argon,where oxygen wa...Ti-6Al-4V alloy powder was prepared through a two-step reduction of a mixture of TiO_(2),V_(2)O_(5) and Al_(2)O_(3) in this study.The oxide mixture was first reduced by Mg in MgCl_(2) at 750℃ in argon,where oxygen was reduced to 2.47 wt%from 40.02 wt%.The oxygen content in the final powder was eventually reduced to an extremely low level(0.055 wt%)using calcium at 900℃ in argon,and the final powder had the composition of 90.12 wt%Ti,5.57 wt%Al,and 3.87 wt%V,which meets the standard specification of Ti-6Al-4V(ASTM F1108-09).Between the two reductions,a heat treatment step was designed to help controlling the specific surface area and particle size.The effect of the heat treatment temperature on the morphology,and composition uniformity of the powder was investigated in detail.Heat treatment above 1300℃ attributed to a dense powder with a controlled specific surface area.Thermodynamic modeling and experimental results indicated that onlyα-Ti enriched with Al andβ-Ti enriched with V exist in the final powder,and other possible phases including Al-Mg and Al-V were excluded.This study also offers a triple-step thermochemical process for producing high-purity Ti-based alloy powder.展开更多
PdAuIr/C-Sb2O5·SnO2electrocatalysts with Pd∶Au∶Ir molar ratios of 90∶5∶5,70∶20∶10 and 50∶45∶5 were prepared by borohydride reduction method.These electrocatalysts were characterized by EDX,X-ray diffracti...PdAuIr/C-Sb2O5·SnO2electrocatalysts with Pd∶Au∶Ir molar ratios of 90∶5∶5,70∶20∶10 and 50∶45∶5 were prepared by borohydride reduction method.These electrocatalysts were characterized by EDX,X-ray diffraction,transmission electron microscopy and the catalytic activity toward formic acid electro-oxidation in acid medium investigated by cyclic voltammetry(CV),chroamperometry(CA)and tests on direct formic acid fuel cell(DFAFC)at 100℃.X-ray diffractograms of PdAuIr/C-Sb2O5·SnO2electrocatalysts showed the presence of Pd fcc phase,Pd-Au fcc alloys,carbon and ATO phases,while Ir phases were not observed.TEM micrographs and histograms indicated that the nanoparticles were not well dispersed on the support and some agglomerates.The cyclic voltammetry and chroamperometry studies showed that PdAuIr/C-Sb2O5·SnO2(50∶45∶5)had superior performance toward formic acid electro-oxidation at 25℃compared to PdAuIr/C-Sb2O5·SnO2(70∶20∶10),PdAuIr/C-Sb2O5·SnO2(90∶5∶5)and Pd/C-Sb2O5·SnO2electrocatalysts.The experiments in a single DFAFC also showed that all PdAuIr/C-Sb2O5·SnO2electrocatalysts exhibited higher performance for formic acid oxidation in comparison with Pd/C-Sb2O5·SnO2electrocatalysts,however PdAuIr/C-Sb2O5·SnO2(90∶5∶5)had superior performance.These results indicated that the addition of Au and Ir to Pd favor the electro-oxidation of formic acid,which could be attributed to the bifunctional mechanism(the presence of ATO,Au and Ir oxides species)associated to the electronic effect(Pd-Au fcc alloys).展开更多
Reduced graphene oxide(RGO) sheets with varied contents and types of oxygenated groups were synthesized by Hummers treatment of natural graphite powders followed by different nontoxic and mild reduction methods, which...Reduced graphene oxide(RGO) sheets with varied contents and types of oxygenated groups were synthesized by Hummers treatment of natural graphite powders followed by different nontoxic and mild reduction methods, which include thermal and chemical reduction with ethylene glycol, KOH and Fe powder. The changes in microstructure and surface chemistry of RGOs were extensively characterized by SEM, TEM, AFM, XRD, XPS and Raman spectrum. The results show that significant exfoliation occurs during oxidation and is retained in reduction processes, along with the formation of curled wavy morphology. Compared with large d spacing(0.852 nm) of graphene oxide(GO), the(002) plane distance decreases to 0.358-0.384 nm of RGOs, indicating efficient tuning of surface functionalities through mild reduction methods. The ID/IG ratio of RGOs is about 1.0-1.15, indicating that reconstructed sp^2 domains have smaller sizes and larger quantity. The content of sp^2 bonded C in GO(36.93%, molar fraction) increases to 45.48%-72.92%(molar fraction) in RGOs, along with a drastic decrease in hydroxyl and epoxy and minor changes in carbonyl and carboxyl. Thermal reduction or chemical reduction produces RGOs with residual functionalities, which may render different chemical activity and is desirable in various applications.展开更多
文摘PtRuIn/C electrocatalysts( 20% metal loading by weight) were prepared by sodium borohydride reduction process using H_2PtCl6·6H_2O,RuCl_3·xH_2O and InCl_3·xH_2O as metal sources,borohydride as reducing agent and Carbon Vulcan XC72 as support. The synthetized PtRuIn/C electrocatalysts were characterized by X-ray diffraction( XRD),energy dispersive analysis( EDX),transmission electron microscopy( TEM),cyclic voltammetry( CV),chronoamperommetry( CA) and polarization curves in alkaline and acidic electrolytes( single cell experiments). The XRD patterns showPtpeaks are attributed to the face-centered cubic( fcc) structure,and a shift of Pt( fcc) peaks indicates that Ru or In is incorporated into Ptlattice. TEMmicrographs showmetal nanoparticles with an average nanoparticle size between 2.7 and 3.5 nm. Methanol oxidation in acidic and alkaline electrolytes was investigated at room temperature,by CV and CA. PtRu/C( 50 ∶ 50) shows the highest activity among all electrocatalysts in study considering methanol oxidation for acidic and alkaline electrolyte. Polarization curves at 80 ℃ showPtRuIn/C( 50 ∶ 25 ∶ 25)with superior performance for methanol oxidation,when compared to Pt/C,PtIn/C and PtRu/C for both electrolytes. The best performance obtained by PtRuIn/C( 50 ∶ 25 ∶ 25) in real conditions could be associated with the increased kinetics reaction and/or with the occurrence simultaneously of the bifunctional mechanism and electronic effect resulting from the presence of Ptalloy.
基金The project was supported by the FAPESP(2014/09087-4,2014/50279-4).
文摘The main objective of this paper was to characterize the voltammetric profiles of the Pt/C,Pt/C-ATO,Pd/C and Pd/CATO electrocatalysts and study their catalytic activities for methane oxidation in an acidic electrolyte at 25 ℃ and in a direct methane proton exchange membrane fuel cell at 80 ℃. The electrocatalysts prepared also were characterized by X-ray diffraction( XRD) and transmission electron microscopy( TEM). The diffractograms of the Pt/C and Pt/C-ATO electrocatalysts show four peaks associated with Pt face-centered cubic( fcc) structure,and the diffractograms of Pd/C and Pd/C-ATO show four peaks associated with Pd face-centered cubic( fcc) structure. For Pt/C-ATO and Pd/C-ATO,characteristic peaks of cassiterite( SnO_2) phase are observed,which are associated with Sb-doped SnO_2( ATO) used as supports for electrocatalysts. Cyclic voltammograms( CV) of all electrocatalysts after adsorption of methane show that there is a current increase during the anodic scan. However,this effect is more pronounced for Pt/C-ATO and Pd/C-ATO. This process is related to the oxidation of the adsorbed species through the bifunctional mechanism,where ATO provides oxygenated species for the oxidation of CO or HCO intermediates adsorbed in Pt or Pd sites. From in situ ATR-FTIR( Attenuated Total Reflectance-Fourier Transform Infrared) experiments for all electrocatalysts prepared the formation of HCO or CO intermediates are observed,which indicates the production of carbon dioxide. Polarization curves at 80 ℃in a direct methane fuel cell( DMEFC) show that Pd/C and Pt/C electroacatalysts have superior performance to Pd/C-ATO and Pt/C-ATO in methane oxidation.
文摘Mining activities have created great wealth, but they have also discharged large quantities of tailings. As an important source of heavy metal contamination, sulfide tailings are usually disposed of in open-air impoundments and thus are exposed to microbial oxidation. Microbial activities greatly enhance sulfide oxidation and result in the release of heavy metals and the precipitation of iron (oxy) hydroxides and sulfates. These secondary minerals in turn influence the mobility of dissolved metals and play important roles in the natural attenuation of heavy metals. Elucidating the microbe–mineral interactions in tailings will improve our understanding of the environmental consequence of mining activities.
基金supported by the Guangxi Natural Science Fund for Distinguished Young Scholars(2024GXNSFFA010008)Shenzhen Science and Technology Program(JCYJ20230807112503008).
文摘Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.
文摘The mineralogical features of the oxidation-reduction of graphite deposit in pingdu, Shandong province were studied by field search, polarization microscope, X-ray diffraction (XRD) and SEM. The results show that, the major rocks of the reduction graphite zone are graphite-quartz anorthosite, gabbro. The major rocks of the oxidation graphite zone are marble with graphite, biotite granite, monzogranite. The main minerals of the reduction zone are plagioclase, pyroxene, quartz, pyrite. The graphite is aphanitic graphite appearing as dense massive, layered, spherical aggregates. The main minerals of the oxidation zone are calcite, quartz, K-feldspar, biotite, amphibole, chlorite. The graphite is flake graphite uniformly dispersed in the loose, and strongly erosion rocks. A large number of rocks in the area have been suffered chloritization, regional metamorphism, indicating that the formation of the graphite deposit should be related with gabbro melting. The carbon source in the lower part was taken into the mine, and then experienced regional metamorphism.
基金Project(52004342) supported by the National Natural Science Foundation of ChinaProject(150240015) supported by the Innovation-Driven Project of Central South University,ChinaProject(2021JJ20065) supported by the Natural Science Fund for Outstanding Young Scholar of Hunan Province,China。
文摘Ti-6Al-4V alloy powder was prepared through a two-step reduction of a mixture of TiO_(2),V_(2)O_(5) and Al_(2)O_(3) in this study.The oxide mixture was first reduced by Mg in MgCl_(2) at 750℃ in argon,where oxygen was reduced to 2.47 wt%from 40.02 wt%.The oxygen content in the final powder was eventually reduced to an extremely low level(0.055 wt%)using calcium at 900℃ in argon,and the final powder had the composition of 90.12 wt%Ti,5.57 wt%Al,and 3.87 wt%V,which meets the standard specification of Ti-6Al-4V(ASTM F1108-09).Between the two reductions,a heat treatment step was designed to help controlling the specific surface area and particle size.The effect of the heat treatment temperature on the morphology,and composition uniformity of the powder was investigated in detail.Heat treatment above 1300℃ attributed to a dense powder with a controlled specific surface area.Thermodynamic modeling and experimental results indicated that onlyα-Ti enriched with Al andβ-Ti enriched with V exist in the final powder,and other possible phases including Al-Mg and Al-V were excluded.This study also offers a triple-step thermochemical process for producing high-purity Ti-based alloy powder.
基金the Laboratório de Microscopia do Centro de Ciências e Tecnologia de Materiais(CCTM) by TEM measurements,FAPESP(2011/18246-0,2012/03516-5) and CNPQ(150639/2013-9)for the financial support
文摘PdAuIr/C-Sb2O5·SnO2electrocatalysts with Pd∶Au∶Ir molar ratios of 90∶5∶5,70∶20∶10 and 50∶45∶5 were prepared by borohydride reduction method.These electrocatalysts were characterized by EDX,X-ray diffraction,transmission electron microscopy and the catalytic activity toward formic acid electro-oxidation in acid medium investigated by cyclic voltammetry(CV),chroamperometry(CA)and tests on direct formic acid fuel cell(DFAFC)at 100℃.X-ray diffractograms of PdAuIr/C-Sb2O5·SnO2electrocatalysts showed the presence of Pd fcc phase,Pd-Au fcc alloys,carbon and ATO phases,while Ir phases were not observed.TEM micrographs and histograms indicated that the nanoparticles were not well dispersed on the support and some agglomerates.The cyclic voltammetry and chroamperometry studies showed that PdAuIr/C-Sb2O5·SnO2(50∶45∶5)had superior performance toward formic acid electro-oxidation at 25℃compared to PdAuIr/C-Sb2O5·SnO2(70∶20∶10),PdAuIr/C-Sb2O5·SnO2(90∶5∶5)and Pd/C-Sb2O5·SnO2electrocatalysts.The experiments in a single DFAFC also showed that all PdAuIr/C-Sb2O5·SnO2electrocatalysts exhibited higher performance for formic acid oxidation in comparison with Pd/C-Sb2O5·SnO2electrocatalysts,however PdAuIr/C-Sb2O5·SnO2(90∶5∶5)had superior performance.These results indicated that the addition of Au and Ir to Pd favor the electro-oxidation of formic acid,which could be attributed to the bifunctional mechanism(the presence of ATO,Au and Ir oxides species)associated to the electronic effect(Pd-Au fcc alloys).
基金Project(51274248)supported by the National Natural Science Foundation of ChinaProjects(2015DFR50580,2013DFA31440)supported by the International Scientific and Technological Cooperation Program of China
文摘Reduced graphene oxide(RGO) sheets with varied contents and types of oxygenated groups were synthesized by Hummers treatment of natural graphite powders followed by different nontoxic and mild reduction methods, which include thermal and chemical reduction with ethylene glycol, KOH and Fe powder. The changes in microstructure and surface chemistry of RGOs were extensively characterized by SEM, TEM, AFM, XRD, XPS and Raman spectrum. The results show that significant exfoliation occurs during oxidation and is retained in reduction processes, along with the formation of curled wavy morphology. Compared with large d spacing(0.852 nm) of graphene oxide(GO), the(002) plane distance decreases to 0.358-0.384 nm of RGOs, indicating efficient tuning of surface functionalities through mild reduction methods. The ID/IG ratio of RGOs is about 1.0-1.15, indicating that reconstructed sp^2 domains have smaller sizes and larger quantity. The content of sp^2 bonded C in GO(36.93%, molar fraction) increases to 45.48%-72.92%(molar fraction) in RGOs, along with a drastic decrease in hydroxyl and epoxy and minor changes in carbonyl and carboxyl. Thermal reduction or chemical reduction produces RGOs with residual functionalities, which may render different chemical activity and is desirable in various applications.
