Due to the dependence of the chemical and physical properties of the bimetallic nanoparticles（NPs） on their structures,a fundamental understanding of their structural characteristics is crucial for their syntheses a...Due to the dependence of the chemical and physical properties of the bimetallic nanoparticles（NPs） on their structures,a fundamental understanding of their structural characteristics is crucial for their syntheses and wide applications. In this article, a systematical atomic-level investigation of Au–Pd bimetallic NPs is conducted by using the improved particle swarm optimization（IPSO） with quantum correction Sutton–Chen potentials（Q-SC） at different Au/Pd ratios and different sizes. In the IPSO, the simulated annealing is introduced into the classical particle swarm optimization（PSO） to improve the effectiveness and reliability. In addition, the influences of initial structure, particle size and composition on structural stability and structural features are also studied. The simulation results reveal that the initial structures have little effects on the stable structures, but influence the converging rate greatly, and the convergence rate of the mixing initial structure is clearly faster than those of the core-shell and phase structures. We find that the Au–Pd NPs prefer the structures with Au-rich in the outer layers while Pd-rich in the inner ones. Especially, when the Au/Pd ratio is 6：4, the structure of the nanoparticle（NP） presents a standardized Pd（core） Au（shell） structure.展开更多
This paper examined the potential of using laboratory-synthesized nanoscale Pd/Fe bimetallic particles to dechlorinate chlorinated methanes, including dichloromethane (DCM), trichloromethane (CF) and tetrachloromethan...This paper examined the potential of using laboratory-synthesized nanoscale Pd/Fe bimetallic particles to dechlorinate chlorinated methanes, including dichloromethane (DCM), trichloromethane (CF) and tetrachloromethane (CT). Nanoscale Pd/Fe bimetallic particles were characterized in terms of surface area, morphology, size and structure. The parameters affecting the dechlorination efficiency were studied through batch experiments. Effects of Pd content, Pd/Fe addition, and the initial pH value of reaction system on the dechlorination efficiency of chlorinated methanes were determined systematically. Results show that nanoscale Pd/Fe bimetallic particles play a prominent role in the dechlorination of chlorinated methanes. The change of pH value and ferrous ion concentration during dechlorination reaction were also investigated in this study. It is found that the dechlorination efficiency of chlorinated methanes is in the order of CT>CF>DCM.展开更多
Nanoscale palladized iron(Pd/Fe)bimetallic particles were prepared by reductive deposition method.The particles were characterized by X-ray diffraction(XRD),X-ray fluorescence(XRF),scanning electron microscope(SEM),tr...Nanoscale palladized iron(Pd/Fe)bimetallic particles were prepared by reductive deposition method.The particles were characterized by X-ray diffraction(XRD),X-ray fluorescence(XRF),scanning electron microscope(SEM),transmission electron microscope(TEM),and Brunauer-Emmett-Teller-nitrogen(BET-N_2)method.Data obtained from those methods indicated that nanoscale Pd/Fe bimetallic particles containedα-Fe^0.Detected Pd to Fe ratio by weight(Pd/Fe ratio)was close to theoretical value. Spherical granules with diame...展开更多
Nanoscale bimetallic Ni/Fe particles were synthesized from the reaction of sodium borohydride （NaBH4） with reduction of Ni^2＋ and Fe^2＋ in aqueous solution. The obtained Ni/Fe particles were characterized by TEM ...Nanoscale bimetallic Ni/Fe particles were synthesized from the reaction of sodium borohydride （NaBH4） with reduction of Ni^2＋ and Fe^2＋ in aqueous solution. The obtained Ni/Fe particles were characterized by TEM （transmission electron microscope）, XRD （X-ray diffractometer）, and N2-BET. The dechlorination activity of the Ni/Fe was investigated using p-chlorophenol （p-CP） as a probe agent. Results demonstrated that the nanoscale Ni/Fe could effectively dechlorinate p-CP at relatively low metal to solution ratio of 0.4 g/L （Ni 5 wt%）. The target with initial concentration ofp-CP 0.625 mmol/L was dechlorinted completely in 60 rain under ambient temperature and pressure. Factors affecting dechlorination efficiency, including reaction temperature, pH, Ni loading percentage over Fe, and metal to solution ratio, were investigated. The possible mechanism of dechlorination ofp-CP was proposed and discussed. The pseudo-first- order reaction took place on the surface of the Ni/Fe bimetallic particles, and the activation energy of the dechlorination reaction was determined to be 21.2 kJ/mol at the temperature rang of 287-313 K.展开更多
In this study, bimetallic nanoscale zero-valent iron particles（nZVI）, including copper/nanoscale zero-valent iron particles（Cu/nZVI） and nickel/nanoscale zero-valent iron particles（Ni/nZVI）, were synthesized by ...In this study, bimetallic nanoscale zero-valent iron particles（nZVI）, including copper/nanoscale zero-valent iron particles（Cu/nZVI） and nickel/nanoscale zero-valent iron particles（Ni/nZVI）, were synthesized by one-step liquid-phase reduction and applied for oxytetracycline（OTC） removal. The effects of contact time and initial p H on the removal efficiency were studied. The as-prepared nanoscale particles were characterized by scanning electron microscopy（SEM）, energy dispersive spectroscopy（EDS） and X-ray diffraction（XRD）. Finally, the degradation mechanisms of OTC utilizing the as-prepared nanoparticles were investigated by using X-ray photoelectron spectroscopy（XPS） and mass spectrometry（MS）. Cu/n ZVI presented remarkable ability for OTC degradation and removed71.44% of OTC（100 mg/L） in 4 hr, while only 62.34% and 31.05% of OTC was degraded by Ni/nZVI and nZVI respectively. XPS and MS analysis suggested that OTC was broken down to form small molecules by ·OH radicals generated from the corrosion of Fe0. Cu/nZVI and Ni/n ZVI have been proved to have potential as materials for application in OTC removal because of their significant degradation ability toward OTC.展开更多
The feasibility of the rapid degradation of hexachlorobenzene （HCB） by micron-size silver （Ag）/iron （Fe） particles was investigated.Ag/Fe particles with different ratios （0,0.05%,0.09%,0.20%,and 0.45%） were pr...The feasibility of the rapid degradation of hexachlorobenzene （HCB） by micron-size silver （Ag）/iron （Fe） particles was investigated.Ag/Fe particles with different ratios （0,0.05%,0.09%,0.20%,and 0.45%） were prepared by electroless silver plating on 300 mesh Fe powder,and were used to degrade HCB at different pH values and temperatures.The dechlorination ability of Fe greatly increased with small Ag addition,whereas too much added Ag would cover the Fe surface and reduce the effective reaction surface,thereby decreasing the extent of dechlorination.The optimal Ag/Fe ratio was 0.09%.Tafel polarization curves showed that HCB was rapidly degraded at neutral or acidic pH,whereas low pH levels severely intensified H2 production,which consumed the reducing electrons needed for the HCB degradation.HCB degradation was more sensitive to temperature than pH.The rate constant of HCB dechlorination was 0.452 min-1 at 85℃,50 times higher than that at 31℃.HCB was degraded in a successive dechlorination pathway,yielding the main products 1,2,4,5-tetrachlorobenzene and 1,2,4-trichlorobenzene within 2 hr.展开更多
Direct synthesis of H_(2)O_(2)from H_(2) and O_(2)via heterogeneous catalysis is an environmentally friendly and atomically economic alternative to the traditional anthraquinone oxidation(AO)process.Optimizing the ele...Direct synthesis of H_(2)O_(2)from H_(2) and O_(2)via heterogeneous catalysis is an environmentally friendly and atomically economic alternative to the traditional anthraquinone oxidation(AO)process.Optimizing the electronic and geometric structures of the active metals to break the current limitations of hydrogenation rate and H_(2)O_(2)selectivity is a promising and challenging topic.In this study,a series of Pd-Au bimetallic catalysts supported on TiO_(2)with a metal loading of 3.0 wt%and a constant Pd/Au molar ratio(Pd:Au=2:1)were prepared.The catalysts were reduced in H_(2) at different temperatures(473,573 and 673 K),and their catalytic activity for the direct H_(2)O_(2)synthesis were evaluated at 283 K and 0.1MPa.H_(2) reduced Pd-Au catalysts exhibited superior performance in direct H_(2)O_(2)synthesis.The maximum H_(2)O_(2)selectivity of 87.7%and H_(2)O_(2)yield of 3116.4 mmol h^(−1) gPd^(−1) were achieved over the Pd_(2.0)Au_(1.0)-573 catalyst with a H_(2) conversion of 12.8%.The tailored local chemical environment caused by H_(2) reduction creates a balanced ratio of Pd0 and PdO_(x) sites,thus improving the selectivity towards H_(2)O_(2).This work developed an effective strategy for fabrication of highly active and stable Pd-based H_(2)O_(2)synthesis catalysts with high H_(2)O_(2)yield.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.11474234 and 61403318)the Fundamental Research Funds for the Central Universities of China(Grant No.20720160085)
文摘Due to the dependence of the chemical and physical properties of the bimetallic nanoparticles（NPs） on their structures,a fundamental understanding of their structural characteristics is crucial for their syntheses and wide applications. In this article, a systematical atomic-level investigation of Au–Pd bimetallic NPs is conducted by using the improved particle swarm optimization（IPSO） with quantum correction Sutton–Chen potentials（Q-SC） at different Au/Pd ratios and different sizes. In the IPSO, the simulated annealing is introduced into the classical particle swarm optimization（PSO） to improve the effectiveness and reliability. In addition, the influences of initial structure, particle size and composition on structural stability and structural features are also studied. The simulation results reveal that the initial structures have little effects on the stable structures, but influence the converging rate greatly, and the convergence rate of the mixing initial structure is clearly faster than those of the core-shell and phase structures. We find that the Au–Pd NPs prefer the structures with Au-rich in the outer layers while Pd-rich in the inner ones. Especially, when the Au/Pd ratio is 6：4, the structure of the nanoparticle（NP） presents a standardized Pd（core） Au（shell） structure.
基金Sponsored by the National Natural Science Foundation of China (Grant No. 50978066)State Key Laboratory of Urban Water Resources and Environment (Grant No.2008DX06)
文摘This paper examined the potential of using laboratory-synthesized nanoscale Pd/Fe bimetallic particles to dechlorinate chlorinated methanes, including dichloromethane (DCM), trichloromethane (CF) and tetrachloromethane (CT). Nanoscale Pd/Fe bimetallic particles were characterized in terms of surface area, morphology, size and structure. The parameters affecting the dechlorination efficiency were studied through batch experiments. Effects of Pd content, Pd/Fe addition, and the initial pH value of reaction system on the dechlorination efficiency of chlorinated methanes were determined systematically. Results show that nanoscale Pd/Fe bimetallic particles play a prominent role in the dechlorination of chlorinated methanes. The change of pH value and ferrous ion concentration during dechlorination reaction were also investigated in this study. It is found that the dechlorination efficiency of chlorinated methanes is in the order of CT>CF>DCM.
文摘Nanoscale palladized iron(Pd/Fe)bimetallic particles were prepared by reductive deposition method.The particles were characterized by X-ray diffraction(XRD),X-ray fluorescence(XRF),scanning electron microscope(SEM),transmission electron microscope(TEM),and Brunauer-Emmett-Teller-nitrogen(BET-N_2)method.Data obtained from those methods indicated that nanoscale Pd/Fe bimetallic particles containedα-Fe^0.Detected Pd to Fe ratio by weight(Pd/Fe ratio)was close to theoretical value. Spherical granules with diame...
基金Project supported by the National Basic Research Program (973) of China(No. 2003CB415006)the National Natural Science Foundation of China (No. 20337020)
文摘Nanoscale bimetallic Ni/Fe particles were synthesized from the reaction of sodium borohydride （NaBH4） with reduction of Ni^2＋ and Fe^2＋ in aqueous solution. The obtained Ni/Fe particles were characterized by TEM （transmission electron microscope）, XRD （X-ray diffractometer）, and N2-BET. The dechlorination activity of the Ni/Fe was investigated using p-chlorophenol （p-CP） as a probe agent. Results demonstrated that the nanoscale Ni/Fe could effectively dechlorinate p-CP at relatively low metal to solution ratio of 0.4 g/L （Ni 5 wt%）. The target with initial concentration ofp-CP 0.625 mmol/L was dechlorinted completely in 60 rain under ambient temperature and pressure. Factors affecting dechlorination efficiency, including reaction temperature, pH, Ni loading percentage over Fe, and metal to solution ratio, were investigated. The possible mechanism of dechlorination ofp-CP was proposed and discussed. The pseudo-first- order reaction took place on the surface of the Ni/Fe bimetallic particles, and the activation energy of the dechlorination reaction was determined to be 21.2 kJ/mol at the temperature rang of 287-313 K.
基金supported by grants from Tai Shan Scholar Foundation(No.ts 201511003)
文摘In this study, bimetallic nanoscale zero-valent iron particles（nZVI）, including copper/nanoscale zero-valent iron particles（Cu/nZVI） and nickel/nanoscale zero-valent iron particles（Ni/nZVI）, were synthesized by one-step liquid-phase reduction and applied for oxytetracycline（OTC） removal. The effects of contact time and initial p H on the removal efficiency were studied. The as-prepared nanoscale particles were characterized by scanning electron microscopy（SEM）, energy dispersive spectroscopy（EDS） and X-ray diffraction（XRD）. Finally, the degradation mechanisms of OTC utilizing the as-prepared nanoparticles were investigated by using X-ray photoelectron spectroscopy（XPS） and mass spectrometry（MS）. Cu/n ZVI presented remarkable ability for OTC degradation and removed71.44% of OTC（100 mg/L） in 4 hr, while only 62.34% and 31.05% of OTC was degraded by Ni/nZVI and nZVI respectively. XPS and MS analysis suggested that OTC was broken down to form small molecules by ·OH radicals generated from the corrosion of Fe0. Cu/nZVI and Ni/n ZVI have been proved to have potential as materials for application in OTC removal because of their significant degradation ability toward OTC.
基金supported by the National High Technology Research and Development Program(863)of China(No.2009AA064001)
文摘The feasibility of the rapid degradation of hexachlorobenzene （HCB） by micron-size silver （Ag）/iron （Fe） particles was investigated.Ag/Fe particles with different ratios （0,0.05%,0.09%,0.20%,and 0.45%） were prepared by electroless silver plating on 300 mesh Fe powder,and were used to degrade HCB at different pH values and temperatures.The dechlorination ability of Fe greatly increased with small Ag addition,whereas too much added Ag would cover the Fe surface and reduce the effective reaction surface,thereby decreasing the extent of dechlorination.The optimal Ag/Fe ratio was 0.09%.Tafel polarization curves showed that HCB was rapidly degraded at neutral or acidic pH,whereas low pH levels severely intensified H2 production,which consumed the reducing electrons needed for the HCB degradation.HCB degradation was more sensitive to temperature than pH.The rate constant of HCB dechlorination was 0.452 min-1 at 85℃,50 times higher than that at 31℃.HCB was degraded in a successive dechlorination pathway,yielding the main products 1,2,4,5-tetrachlorobenzene and 1,2,4-trichlorobenzene within 2 hr.
基金supported by the National Natural Science Foundation of China(Nos.91934302 and 22178110)the Dean/Opening Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(No.2020K001)the Project of the Department of Science and Technology of Sichuan Province(No.2023YFQ0086).
文摘Direct synthesis of H_(2)O_(2)from H_(2) and O_(2)via heterogeneous catalysis is an environmentally friendly and atomically economic alternative to the traditional anthraquinone oxidation(AO)process.Optimizing the electronic and geometric structures of the active metals to break the current limitations of hydrogenation rate and H_(2)O_(2)selectivity is a promising and challenging topic.In this study,a series of Pd-Au bimetallic catalysts supported on TiO_(2)with a metal loading of 3.0 wt%and a constant Pd/Au molar ratio(Pd:Au=2:1)were prepared.The catalysts were reduced in H_(2) at different temperatures(473,573 and 673 K),and their catalytic activity for the direct H_(2)O_(2)synthesis were evaluated at 283 K and 0.1MPa.H_(2) reduced Pd-Au catalysts exhibited superior performance in direct H_(2)O_(2)synthesis.The maximum H_(2)O_(2)selectivity of 87.7%and H_(2)O_(2)yield of 3116.4 mmol h^(−1) gPd^(−1) were achieved over the Pd_(2.0)Au_(1.0)-573 catalyst with a H_(2) conversion of 12.8%.The tailored local chemical environment caused by H_(2) reduction creates a balanced ratio of Pd0 and PdO_(x) sites,thus improving the selectivity towards H_(2)O_(2).This work developed an effective strategy for fabrication of highly active and stable Pd-based H_(2)O_(2)synthesis catalysts with high H_(2)O_(2)yield.
