MgH_(2)is a promising solid-state hydrogen storage material.However,its high thermodynamics and sluggish kinetics hinder its practical application.Catalytic strategy is effective in improving its kinetic performance.N...MgH_(2)is a promising solid-state hydrogen storage material.However,its high thermodynamics and sluggish kinetics hinder its practical application.Catalytic strategy is effective in improving its kinetic performance.Nevertheless,the highly efficient catalysts or additives are normally of low-yield in fabrication with high cost.In this work,a novel structural LaVO_(4)fabricated by a low-cost method of spraying dry followed by a calcination is used as a catalytic additive for the hydrogen storage of MgH_(2).With an optimized addition of LaVO_(4),the overall hydrogen storage performances of MgH_(2)are significantly improved.An onset dehydrogenation temperature of only 183℃is obtained after an initial activation of dehydrogenation and hydrogenation.The system can desorb 5.7 wt%H_(2)at 250℃within 10 min and maintains a dehydrogenation capacity of 5.0 wt%H_(2)after 50 cycles.It is found that LaVO_(4)is transferred to lanthanum hydride and metallic vanadium in the initial dehydrogenation process,the former acts as a highly effective catalyst for the hydrogen storage of MgH_(2)and the latter undergoes reversible hydrogenation and dehydrogenation in the subsequent cycles.The structural design of the catalyst and its scalable fabrication are highly valuable in realizing the practical application of catalytic strategy for the hydrogen storage of MgH_(2).展开更多
To address the issues of energy crisis and global warming, novel renewable carbon-free or carbon-neutral energy sources must be identified and developed. A deeper understanding of photosynthesis is the key to provide ...To address the issues of energy crisis and global warming, novel renewable carbon-free or carbon-neutral energy sources must be identified and developed. A deeper understanding of photosynthesis is the key to provide a solid foundation to facilitate this transformation. To mimic the water oxidation of photosystem II oxygen evolving complex, Mn-oxo complexes and Co-phosphate catalytic material were discovered in solar energy storage. Building on these discoveries, recent advances in solar energy conversion showed a compelling working principle by combing the active Mn-oxo and Co-based catalysts in water splitting with semiconductor heteronanostructures for effective solar energy harnessing. In this review the appealing systems including Mn-oxo tetramer/Nafion, Mn-oxo dimer/TiO2, Mn-oxo oligomer/WO3, Co-Pi/Fe2O3, and Co-Pi/ZnO are summarized and discussed. These accomplishments offer a promising framework and have a profound impact in the field of solar fuel production.展开更多
The hydrogen oxidation reaction(HOR)in alkaline conditions is of great importance for the application of anion exchange membrane fuel cells(AEMFCs).However,the electrocatalysts for alkaline HOR generally suffer from t...The hydrogen oxidation reaction(HOR)in alkaline conditions is of great importance for the application of anion exchange membrane fuel cells(AEMFCs).However,the electrocatalysts for alkaline HOR generally suffer from the disadvantage of sluggish kinetics.Herein,we have fabricated Ru2Ni multilayered nanosheets(Ru2Ni MLNSs)in the layer-by-layer manner and engineered the surface properties via postannealing for efficient alkaline HOR.Detailed investigations reveal that such annealing at different temperatures can alter the surface properties of Ru2Ni MLNSs and thus regulate their adsorption abilities toward*H and*OH.In particular,the optimal catalyst exhibits a mass activity of 4.34 A mgRu−1 at an overpotential of 50 mV,which is 18.1 and 13.2 times higher than those of Ru/C(0.24 A mgRu−1)and Pt/C(0.33 A mgPt−1),respectively.Theoretical calculations indicate that the presence of surface O atoms can facilitate the HOR activity while the excessive coverage of O atoms on Ru2Ni surface leads to the strengthened H binding and the decay of HOR activity.This work not only provides an efficient catalyst for alkaline HOR,but it also may shed new light on the design of high-performance catalysts for electrocatalysis and beyond.We have fabricated Ru2Ni multilayer nanosheets(Ru2Ni MLNSs)and realized the surface engineering via an annealing process.Detailed investigations show that such surface engineering can regulate the surface properties and thus promote the alkaline HOR activity.Consequently,the optimal catalyst exhibits a much higher activity than those of commercial Ru/C and Pt/C and is a promising catalyst for alkaline HOR.展开更多
The oxidation of pnitrotoluene with electro-generated superoxide ion in the presence or absence of metallo-porphyrins FeTPP, MnTPP and CoTPP in DMF was studied by cyclic voltammetry and controlled potential electrolys...The oxidation of pnitrotoluene with electro-generated superoxide ion in the presence or absence of metallo-porphyrins FeTPP, MnTPP and CoTPP in DMF was studied by cyclic voltammetry and controlled potential electrolysis, Metallo-porphyrins as catalysts for electroreduction of O_2, they can not only increase yields of p-nitrobensoic acid and selectivities of reaction but also enable the reaction proceed at lower negative potential.展开更多
Oxidative catalysis enables lignin depolymerization to yield carbonyl-containing aromatic chemicals for sustainable lignocellulose valorization.The oxidative depolymerization of lignin requires high oxygen pressure an...Oxidative catalysis enables lignin depolymerization to yield carbonyl-containing aromatic chemicals for sustainable lignocellulose valorization.The oxidative depolymerization of lignin requires high oxygen pressure and harsh conditions to trade off lignin’s structural complexity and limited solubility.Herein,we developed an oxidation system for lignin depolymerization using a single phosphomolybdic acid(H_(3)PMo_(12)O_(40))catalyst in acetic acid solvent to address the aforementioned issues.The entire catalytic system was operated under only 0.1 MPa O_(2) pressure,providing over 20 wt% of aromatic compounds containing aldehydes and carboxylic acids.Theoretical calculations combined with experimental analyses reveal structural transformations and redox behavior driven by the synergistic interaction between H_(3)PMo_(12)O_(40) and acetic acid.Mechanistic studies detected superoxide radicals,confirming the joint role of catalyst and solvent in oxygen activation,radicals stabilization,and enhanced reaction efficiency.A low-cost,commercially available catalyst with minimal oxygen demand offers a promising route to industrial-scale biomass refining.展开更多
The oxidation of exposed pyrite causes acid mine drainage, soil acidification, and the release of toxic metal ions. As the important abiotic oxidants in supergene environments,oxygen and manganese oxides participate i...The oxidation of exposed pyrite causes acid mine drainage, soil acidification, and the release of toxic metal ions. As the important abiotic oxidants in supergene environments,oxygen and manganese oxides participate in the oxidation of pyrite. In this work, the oxidation processes of natural pyrite by oxygen and birnessite were studied in simulated systems, and the influence of p H, Fe（II） and Cr（III） on the intermediates and redox rate was investigated. SO42-and elemental S were formed as the major and minor products,respectively, during the oxidation processes. Ferric（hydr） oxides including Fe（OH）3and goethite were formed with low degree of crystallinity. Low p H and long-term reaction facilitated the formation of goethite and ferric hydroxide, respectively. The rate of pyrite oxidation by birnessite was enhanced in the presence of air（oxygen）, and Fe（II） ions played a key role in the redox process. The addition of Fe（II） ions to the reaction system significantly enhanced the oxidation rate of pyrite; however, the presence of Cr（III） ions remarkably decreased the pyrite oxidation rate in aqueous systems. The introduction of Fe（II） ions to form a Fe（III）/Fe（II） redox couple facilitated the electron transfer and accelerated the oxidation rate of pyrite. The present work suggests that isolation from air and decreasing the concentration of Fe（II） ions in aqueous solutions might be effective strategies to reduce the oxidation rate of pyrite in mining soils.展开更多
By screening the copper catalysts,ligands,and the reaction conditions,a simple CuCl/DMEDA/TEMPO catalyst system readily available from commercial sources is developed for a direct and selective synthesis of the useful...By screening the copper catalysts,ligands,and the reaction conditions,a simple CuCl/DMEDA/TEMPO catalyst system readily available from commercial sources is developed for a direct and selective synthesis of the useful nitriles by an aerobic oxidation reaction of primary amines using air as an advantageous oxidant under mild conditions.展开更多
Wet air oxidation （WAO） and catalytic wet air oxidation （CWAO） of slaughtered animal byproducts （ABPs） were investigated. Two step experiment was carried out consisting of a non-catalysed WAO run followed by a C...Wet air oxidation （WAO） and catalytic wet air oxidation （CWAO） of slaughtered animal byproducts （ABPs） were investigated. Two step experiment was carried out consisting of a non-catalysed WAO run followed by a CWAO run at 170-275 ℃, 20 MPa, and reaction time 180 min. The WAO （lst step） of sample （5 g/L total organic carbon （TOC）） yielded （82.0 ±4）% TOC removal and （78.4 ± 13.2）% conversion of the initial organic-N into NH4＋-N. Four metal catalysts （Pd, Pt, Rh, Ru） supported over alumina have been tested in catalytic WAO （2nd step） at elevated pH to enhance ammonia conversion and organic matter removal, particularly acetic acid. It was found that the catalysts Ru, Pt, and Rh had significant effects on the TOC removal （95.1%, 99.5% and 96.7%, respectively） and on the abatement of ammonia （93.4%, 96.7% and 96.3%, respectively） with high nitrogen selectivity. The catalyst Pd was found to have the less activity while Pt had the best performance. The X-Ray diffraction analysis showed that the support of catalyst was not stable under the experimental conditions since it reacted with phosphate present in solution. Nitrite and nitrate ions were monitored during the oxidation reaction and it was concluded that CWAO of ammonia in real waste treatment framework was in good agreement with the results obtained from the literature for ideal solutions of ammonia.展开更多
A lacunary Keggin-type tungstosilicate dimer-estertin derivative,(C(NH_(2))_(3))_(7)H_(3.5)[(K⊂Ni H_(2)O)_(2)(SnCH_(2)CH_(2)COO)((Ni(H_(2)O))_(0.75)(WO)_(0.25))(Si_(2)W_(18)O_(67))]·6H_(2)O(abbreviated as Si_(2)W...A lacunary Keggin-type tungstosilicate dimer-estertin derivative,(C(NH_(2))_(3))_(7)H_(3.5)[(K⊂Ni H_(2)O)_(2)(SnCH_(2)CH_(2)COO)((Ni(H_(2)O))_(0.75)(WO)_(0.25))(Si_(2)W_(18)O_(67))]·6H_(2)O(abbreviated as Si_(2)W_(18)-Ni-SnRCOO,R=CH_(2)CH_(2)),was synthesized by using the conventional aqueous solution method,and characterized by a series of physical and spectral methods.Single crystal X-ray structural analysis revealed that the polyoxometalate(POM)was a dimeric tungstosilicate-based organic-inorganic hybrid compound,which contained two Ni ions and a cyclic carboxyltin group(SnRCOO).Unexpectedly,the carboxyl-oxygen atom of SnRCOO acted as a bridging oxygen atom belonged to the POM skeleton and connected to NiO_(6)octahedron.The thermal and photocatalytic activities of Si_(2)W_(18)-Ni-SnRCOO were studied.As a homogeneous catalyst,the conversion of cyclohexanol to cyclohexanone was as high as 98%,and the degradation efficiency of 20 mg·L^(-1)RhB reached 88%.The experimental results showed that the introduction of the carboxyethyltin group significantly enhanced the catalytic activity of this type of POM-based catalyst.Additionally,the composite of Si_(2)W_(18)-Ni-SnRCOO and TiO_(2) enabled the catalyst to be recycled,and the photocatalytic efficiency of Si_(2)W_(18)-Ni-SnRCOO/TiO_(2) remained almost unchanged after five cycles.展开更多
Fine particles of zinc-cerium oxides （ZCO） used as an ultraviolet filter were prepared via combustion synthesis route. The catalytic activity, UV-shielding performance, surface modification and application of ZCO in...Fine particles of zinc-cerium oxides （ZCO） used as an ultraviolet filter were prepared via combustion synthesis route. The catalytic activity, UV-shielding performance, surface modification and application of ZCO in polyester varnish were discussed in detail. The experimental results indicate that the photo-catalytic activity of ZCO is much smaller than these of ZnO and TiO2; the oxidation catalytic activity of ZCO is far lower than that of CeO2; the ZCO has shown excellent ultraviolet absorption in the range of UV; addition modified ZCO （MZCO） into polyester will enhance the UV-shielding capability of polyester.展开更多
High-purity of hydrogen is vital to the guarantee of end usage in proton exchange membrane fuel cell(PEMFC)electric vehicles(EVs)with superior durability and low expense.However,the currently employed hydrogen,primari...High-purity of hydrogen is vital to the guarantee of end usage in proton exchange membrane fuel cell(PEMFC)electric vehicles(EVs)with superior durability and low expense.However,the currently employed hydrogen,primarily from fossil fuel,still contains some poisoning impurities that significantly affect the durability of PEMFCs.Here,we investigate the poisoning effect of several typical hydrogen impurities(S^(2-),Cl^(-),HCOO^(-)and CO_(3)^(2-))on the hydrogen oxidation reaction(HOR)of the state-of-the-art carbon-supported platinum(Pt/C)catalyst used in the PEMFC anode.Electrochemical results indicate that the electrochemically active surface area of Pt/C is hampered by these hydrogen impurities with reduced effective Pt reactive sites due to the competitive adsorption against hydrogen at Pt sites showing the extent of the poisoning on Pt sites in the order:S^(2-)>Cl^(-)>HCOO^(-)>CO_(3)^(2-).Density functional theory calculations reveal that the adsorption energy of S2-on Pt(111)is greater than that of Cl^(-),HCOO^(-)and CO_(2),and the electronic structure of Pt is found to be changed due to the adsorption of impurities showing the downshift of the d-band centre of Pt that weakens the adsorption of hydrogen on the Pt sites.This work provides valuable guidance for future optimization of hydrogen quality and also emphasizes the importance of anti-poisoning anode catalyst development,especially towards H_(2)S impurities that seriously affect the durability of PEMFCs.展开更多
A mild and highly efficient amine-catalyzed, IBX-mediated oxidation of aldehydes to （E） selective a, β-unsamrated aldehydes has been achieved in good yields. The process features a new oxidation of enamines to imin...A mild and highly efficient amine-catalyzed, IBX-mediated oxidation of aldehydes to （E） selective a, β-unsamrated aldehydes has been achieved in good yields. The process features a new oxidation of enamines to iminium ions in a catalytic fashion.展开更多
The liquid-phase oxidation of ethylamine with hydrogen peroxide was studied over tungsten-doped zeolites to develop a clean and simple route for producing acetaldehyde oxime. The investigations were firstly performed ...The liquid-phase oxidation of ethylamine with hydrogen peroxide was studied over tungsten-doped zeolites to develop a clean and simple route for producing acetaldehyde oxime. The investigations were firstly performed over W/MOR, where the coordinated state as well as the acidity of the W species were characterized. The reaction parameters, including H_2O_2 amount, solvent,temperature, tungsten content as well as catalyst amount, governed the activity and oxime selectivity. Under optimized reaction conditions, W/MOR showed an ethylamine conversion and corresponding oxime selectivity of 18.3% and 88.9%. W/MOR showed a superior performance in comparison to other tungsten-containing zeolites of W/Beta, W/MWW and W/Y. Although W/MOR exhibited lower amine conversion than titanosilicates of TS-1 and Ti-MWW, it gave higher selectivity to the main product of oxime. Moreover, W/MOR proved to be a robust catalyst, exhibiting a stable catalytic performance after being reused at least for 5 times.展开更多
lnkjet printing （IJP） synthesis has emerged as a useful technique for the fabrication of functional metal oxides in the fields of nanotechnology and materials science. In this paper, we will review the fundamental s...lnkjet printing （IJP） synthesis has emerged as a useful technique for the fabrication of functional metal oxides in the fields of nanotechnology and materials science. In this paper, we will review the fundamental state-of-the-art principles of the special ink formulations used for IJP synthesis of functional metal oxides and the applications of these oxides.展开更多
基金supported by the National Natural Science Foundation of PR China(Nos.52071287,52125104 and 52072342)Natural Science Foundation of Zhejiang Province,PR China(No.LZ23E010002).
文摘MgH_(2)is a promising solid-state hydrogen storage material.However,its high thermodynamics and sluggish kinetics hinder its practical application.Catalytic strategy is effective in improving its kinetic performance.Nevertheless,the highly efficient catalysts or additives are normally of low-yield in fabrication with high cost.In this work,a novel structural LaVO_(4)fabricated by a low-cost method of spraying dry followed by a calcination is used as a catalytic additive for the hydrogen storage of MgH_(2).With an optimized addition of LaVO_(4),the overall hydrogen storage performances of MgH_(2)are significantly improved.An onset dehydrogenation temperature of only 183℃is obtained after an initial activation of dehydrogenation and hydrogenation.The system can desorb 5.7 wt%H_(2)at 250℃within 10 min and maintains a dehydrogenation capacity of 5.0 wt%H_(2)after 50 cycles.It is found that LaVO_(4)is transferred to lanthanum hydride and metallic vanadium in the initial dehydrogenation process,the former acts as a highly effective catalyst for the hydrogen storage of MgH_(2)and the latter undergoes reversible hydrogenation and dehydrogenation in the subsequent cycles.The structural design of the catalyst and its scalable fabrication are highly valuable in realizing the practical application of catalytic strategy for the hydrogen storage of MgH_(2).
基金supported by the University of Massachusetts Dartmouth and in part by a grant from the USDA CSREES
文摘To address the issues of energy crisis and global warming, novel renewable carbon-free or carbon-neutral energy sources must be identified and developed. A deeper understanding of photosynthesis is the key to provide a solid foundation to facilitate this transformation. To mimic the water oxidation of photosystem II oxygen evolving complex, Mn-oxo complexes and Co-phosphate catalytic material were discovered in solar energy storage. Building on these discoveries, recent advances in solar energy conversion showed a compelling working principle by combing the active Mn-oxo and Co-based catalysts in water splitting with semiconductor heteronanostructures for effective solar energy harnessing. In this review the appealing systems including Mn-oxo tetramer/Nafion, Mn-oxo dimer/TiO2, Mn-oxo oligomer/WO3, Co-Pi/Fe2O3, and Co-Pi/ZnO are summarized and discussed. These accomplishments offer a promising framework and have a profound impact in the field of solar fuel production.
基金gratefully acknowledge the financial support of the National Key R&D Program of China(grant no.2020YFB1505802)the Ministry of Science and Technology of China(grant no.2017YFA0208200)+3 种基金the National Natural Science Foundation of China(grant nos.22025108,U21A20327,and 22121001)the China Postdoctoral Science Foundation(grant no.2020M682083)Guangdong Provincial Natural Science Fund for Distinguished Young Scholars(grant no.2021B1515020081)start-up support from Xiamen University.
文摘The hydrogen oxidation reaction(HOR)in alkaline conditions is of great importance for the application of anion exchange membrane fuel cells(AEMFCs).However,the electrocatalysts for alkaline HOR generally suffer from the disadvantage of sluggish kinetics.Herein,we have fabricated Ru2Ni multilayered nanosheets(Ru2Ni MLNSs)in the layer-by-layer manner and engineered the surface properties via postannealing for efficient alkaline HOR.Detailed investigations reveal that such annealing at different temperatures can alter the surface properties of Ru2Ni MLNSs and thus regulate their adsorption abilities toward*H and*OH.In particular,the optimal catalyst exhibits a mass activity of 4.34 A mgRu−1 at an overpotential of 50 mV,which is 18.1 and 13.2 times higher than those of Ru/C(0.24 A mgRu−1)and Pt/C(0.33 A mgPt−1),respectively.Theoretical calculations indicate that the presence of surface O atoms can facilitate the HOR activity while the excessive coverage of O atoms on Ru2Ni surface leads to the strengthened H binding and the decay of HOR activity.This work not only provides an efficient catalyst for alkaline HOR,but it also may shed new light on the design of high-performance catalysts for electrocatalysis and beyond.We have fabricated Ru2Ni multilayer nanosheets(Ru2Ni MLNSs)and realized the surface engineering via an annealing process.Detailed investigations show that such surface engineering can regulate the surface properties and thus promote the alkaline HOR activity.Consequently,the optimal catalyst exhibits a much higher activity than those of commercial Ru/C and Pt/C and is a promising catalyst for alkaline HOR.
文摘The oxidation of pnitrotoluene with electro-generated superoxide ion in the presence or absence of metallo-porphyrins FeTPP, MnTPP and CoTPP in DMF was studied by cyclic voltammetry and controlled potential electrolysis, Metallo-porphyrins as catalysts for electroreduction of O_2, they can not only increase yields of p-nitrobensoic acid and selectivities of reaction but also enable the reaction proceed at lower negative potential.
文摘Oxidative catalysis enables lignin depolymerization to yield carbonyl-containing aromatic chemicals for sustainable lignocellulose valorization.The oxidative depolymerization of lignin requires high oxygen pressure and harsh conditions to trade off lignin’s structural complexity and limited solubility.Herein,we developed an oxidation system for lignin depolymerization using a single phosphomolybdic acid(H_(3)PMo_(12)O_(40))catalyst in acetic acid solvent to address the aforementioned issues.The entire catalytic system was operated under only 0.1 MPa O_(2) pressure,providing over 20 wt% of aromatic compounds containing aldehydes and carboxylic acids.Theoretical calculations combined with experimental analyses reveal structural transformations and redox behavior driven by the synergistic interaction between H_(3)PMo_(12)O_(40) and acetic acid.Mechanistic studies detected superoxide radicals,confirming the joint role of catalyst and solvent in oxygen activation,radicals stabilization,and enhanced reaction efficiency.A low-cost,commercially available catalyst with minimal oxygen demand offers a promising route to industrial-scale biomass refining.
基金supported by the National Natural Science Foundation of China (Nos: 41171375, 41171364 and 41571228)the Program for New Century Excellent Talents in University of China (No. NCET-12-0862)+2 种基金the Fok Ying-Tong Education Foundation (No. 141024)the Natural Science Foundation of Hubei Province of China (No: 2012FFA031, 2014CFA016)the Fundamental Research Funds for the Central Universities (Nos.: 2662015JQ002, 2013PY029, 2013PY030)
文摘The oxidation of exposed pyrite causes acid mine drainage, soil acidification, and the release of toxic metal ions. As the important abiotic oxidants in supergene environments,oxygen and manganese oxides participate in the oxidation of pyrite. In this work, the oxidation processes of natural pyrite by oxygen and birnessite were studied in simulated systems, and the influence of p H, Fe（II） and Cr（III） on the intermediates and redox rate was investigated. SO42-and elemental S were formed as the major and minor products,respectively, during the oxidation processes. Ferric（hydr） oxides including Fe（OH）3and goethite were formed with low degree of crystallinity. Low p H and long-term reaction facilitated the formation of goethite and ferric hydroxide, respectively. The rate of pyrite oxidation by birnessite was enhanced in the presence of air（oxygen）, and Fe（II） ions played a key role in the redox process. The addition of Fe（II） ions to the reaction system significantly enhanced the oxidation rate of pyrite; however, the presence of Cr（III） ions remarkably decreased the pyrite oxidation rate in aqueous systems. The introduction of Fe（II） ions to form a Fe（III）/Fe（II） redox couple facilitated the electron transfer and accelerated the oxidation rate of pyrite. The present work suggests that isolation from air and decreasing the concentration of Fe（II） ions in aqueous solutions might be effective strategies to reduce the oxidation rate of pyrite in mining soils.
基金NNSFC(Nos.51502174,21672163)ZJNSF(No.LR14B020002)+2 种基金Postdoctoral Science Foundation of China(Nos.2015 M582401,2016M592520)for financial supportpartially supported by Science and Technology Project of Shenzhen(Nos.JCYJ20150324141711616,JCYJ20150626090504916)Science and Technology Planning Project of Guangdong Province(No.2016B050501005)
文摘By screening the copper catalysts,ligands,and the reaction conditions,a simple CuCl/DMEDA/TEMPO catalyst system readily available from commercial sources is developed for a direct and selective synthesis of the useful nitriles by an aerobic oxidation reaction of primary amines using air as an advantageous oxidant under mild conditions.
基金supported by l'agence de l'environnement et de la maitrise de l'nergie (ADEME) (research contract 0372C0028)the French Ministry of Research ACI DEBIOCIDE-ECD010
文摘Wet air oxidation （WAO） and catalytic wet air oxidation （CWAO） of slaughtered animal byproducts （ABPs） were investigated. Two step experiment was carried out consisting of a non-catalysed WAO run followed by a CWAO run at 170-275 ℃, 20 MPa, and reaction time 180 min. The WAO （lst step） of sample （5 g/L total organic carbon （TOC）） yielded （82.0 ±4）% TOC removal and （78.4 ± 13.2）% conversion of the initial organic-N into NH4＋-N. Four metal catalysts （Pd, Pt, Rh, Ru） supported over alumina have been tested in catalytic WAO （2nd step） at elevated pH to enhance ammonia conversion and organic matter removal, particularly acetic acid. It was found that the catalysts Ru, Pt, and Rh had significant effects on the TOC removal （95.1%, 99.5% and 96.7%, respectively） and on the abatement of ammonia （93.4%, 96.7% and 96.3%, respectively） with high nitrogen selectivity. The catalyst Pd was found to have the less activity while Pt had the best performance. The X-Ray diffraction analysis showed that the support of catalyst was not stable under the experimental conditions since it reacted with phosphate present in solution. Nitrite and nitrate ions were monitored during the oxidation reaction and it was concluded that CWAO of ammonia in real waste treatment framework was in good agreement with the results obtained from the literature for ideal solutions of ammonia.
基金financially supported by the National Natural Science Foundation of China (21671091 and 21503103)the Startup Project of Doctor Scientific Research from Liaoning Normal University (2023BSL017)
文摘A lacunary Keggin-type tungstosilicate dimer-estertin derivative,(C(NH_(2))_(3))_(7)H_(3.5)[(K⊂Ni H_(2)O)_(2)(SnCH_(2)CH_(2)COO)((Ni(H_(2)O))_(0.75)(WO)_(0.25))(Si_(2)W_(18)O_(67))]·6H_(2)O(abbreviated as Si_(2)W_(18)-Ni-SnRCOO,R=CH_(2)CH_(2)),was synthesized by using the conventional aqueous solution method,and characterized by a series of physical and spectral methods.Single crystal X-ray structural analysis revealed that the polyoxometalate(POM)was a dimeric tungstosilicate-based organic-inorganic hybrid compound,which contained two Ni ions and a cyclic carboxyltin group(SnRCOO).Unexpectedly,the carboxyl-oxygen atom of SnRCOO acted as a bridging oxygen atom belonged to the POM skeleton and connected to NiO_(6)octahedron.The thermal and photocatalytic activities of Si_(2)W_(18)-Ni-SnRCOO were studied.As a homogeneous catalyst,the conversion of cyclohexanol to cyclohexanone was as high as 98%,and the degradation efficiency of 20 mg·L^(-1)RhB reached 88%.The experimental results showed that the introduction of the carboxyethyltin group significantly enhanced the catalytic activity of this type of POM-based catalyst.Additionally,the composite of Si_(2)W_(18)-Ni-SnRCOO and TiO_(2) enabled the catalyst to be recycled,and the photocatalytic efficiency of Si_(2)W_(18)-Ni-SnRCOO/TiO_(2) remained almost unchanged after five cycles.
基金the Nation Ministry Education Scientific Research Fund for Study Abroad Returnee([2004]527)
文摘Fine particles of zinc-cerium oxides （ZCO） used as an ultraviolet filter were prepared via combustion synthesis route. The catalytic activity, UV-shielding performance, surface modification and application of ZCO in polyester varnish were discussed in detail. The experimental results indicate that the photo-catalytic activity of ZCO is much smaller than these of ZnO and TiO2; the oxidation catalytic activity of ZCO is far lower than that of CeO2; the ZCO has shown excellent ultraviolet absorption in the range of UV; addition modified ZCO （MZCO） into polyester will enhance the UV-shielding capability of polyester.
基金supported by the National Key R&D Program of China (No.2019YFB1505004).
文摘High-purity of hydrogen is vital to the guarantee of end usage in proton exchange membrane fuel cell(PEMFC)electric vehicles(EVs)with superior durability and low expense.However,the currently employed hydrogen,primarily from fossil fuel,still contains some poisoning impurities that significantly affect the durability of PEMFCs.Here,we investigate the poisoning effect of several typical hydrogen impurities(S^(2-),Cl^(-),HCOO^(-)and CO_(3)^(2-))on the hydrogen oxidation reaction(HOR)of the state-of-the-art carbon-supported platinum(Pt/C)catalyst used in the PEMFC anode.Electrochemical results indicate that the electrochemically active surface area of Pt/C is hampered by these hydrogen impurities with reduced effective Pt reactive sites due to the competitive adsorption against hydrogen at Pt sites showing the extent of the poisoning on Pt sites in the order:S^(2-)>Cl^(-)>HCOO^(-)>CO_(3)^(2-).Density functional theory calculations reveal that the adsorption energy of S2-on Pt(111)is greater than that of Cl^(-),HCOO^(-)and CO_(2),and the electronic structure of Pt is found to be changed due to the adsorption of impurities showing the downshift of the d-band centre of Pt that weakens the adsorption of hydrogen on the Pt sites.This work provides valuable guidance for future optimization of hydrogen quality and also emphasizes the importance of anti-poisoning anode catalyst development,especially towards H_(2)S impurities that seriously affect the durability of PEMFCs.
基金the financial support from the National Science Foun-dation (CHE-1057569,W. W.)the China 111 Project (B07023,J. L. and W. W.)+1 种基金the National Natural Science Foundation of China (20972051,X. Y.-H.)the Science and Technology Commission of Shanghai Mu-nicipality (08430703900 & 08431901800,X. Y.-H.)
文摘A mild and highly efficient amine-catalyzed, IBX-mediated oxidation of aldehydes to （E） selective a, β-unsamrated aldehydes has been achieved in good yields. The process features a new oxidation of enamines to iminium ions in a catalytic fashion.
基金supported by the National Natural Science Foundation of China(21533002,21373089,21603075)the National Key Research and Development Program of China(2016YFA0202804)
文摘The liquid-phase oxidation of ethylamine with hydrogen peroxide was studied over tungsten-doped zeolites to develop a clean and simple route for producing acetaldehyde oxime. The investigations were firstly performed over W/MOR, where the coordinated state as well as the acidity of the W species were characterized. The reaction parameters, including H_2O_2 amount, solvent,temperature, tungsten content as well as catalyst amount, governed the activity and oxime selectivity. Under optimized reaction conditions, W/MOR showed an ethylamine conversion and corresponding oxime selectivity of 18.3% and 88.9%. W/MOR showed a superior performance in comparison to other tungsten-containing zeolites of W/Beta, W/MWW and W/Y. Although W/MOR exhibited lower amine conversion than titanosilicates of TS-1 and Ti-MWW, it gave higher selectivity to the main product of oxime. Moreover, W/MOR proved to be a robust catalyst, exhibiting a stable catalytic performance after being reused at least for 5 times.
基金the National Natural Science Foundation of China(grant Nos.21222307,21271153,51222202,J1210042 and 21003106)the Fok Ying Tung Education Foundation(grant No.131015)+1 种基金the Zhejiang Provincial Natural Science Foundation of China(grant No.R12B030002)the Fundamental Research Funds for the Central Universities(grant No.2012QNA3014) for their financial support
文摘lnkjet printing （IJP） synthesis has emerged as a useful technique for the fabrication of functional metal oxides in the fields of nanotechnology and materials science. In this paper, we will review the fundamental state-of-the-art principles of the special ink formulations used for IJP synthesis of functional metal oxides and the applications of these oxides.
