lmprovement of the charge separation of titanosilicate molecular sieves is critical to their use asphotocatalysts for oxidative organic transformations.In this work,MFI TS-1 molecular sievenanosheets(TS-1 NS)were synt...lmprovement of the charge separation of titanosilicate molecular sieves is critical to their use asphotocatalysts for oxidative organic transformations.In this work,MFI TS-1 molecular sievenanosheets(TS-1 NS)were synthesized by a low-temperature hydrothermal method using a tai-lored diquaternary ammonium surfactant as the structure-directing agent.Introducing Ni^2+cationsat the ion-exchange sites of the TS-1 NS framework significantly enhanced its photoactivity in aero-bic alcohol oxidation.The optimized Ni cation-functionalized TS-1 NS(Ni/TS-1 NS)provide impres-sive photoactivity,with a benzyl alcohol(BA)conversion of 78.9%and benzyl aldehyde(BAD)se-lectivity of 98.8%using O as the only oxidant under full light irradiation;this BAD yield is approx-imately six times greater than that obtained for bulk TS-1,and is maintained for five runs.The ex-cellent photoactivity of Ni/TS-1 NS is attributed to the significantly enlarged surface area of thetwo-dimensional morphology TS-1 NS,extra mesopores,and greatly improved charge separation.Compared with bulk TS-1,Ni/TS-1 NS has a much shorter charge transfer distance.Theas-introduced Ni species could capture the photoelectrons to further improve the charge separa-tion.This work opens the way to a class of highly selective,robust,and low-cost titanosilicate mo-lecular sieve-based photocatalysts with industrial potential for selective oxidative transformationsand pollutant degradation.展开更多
This paper reports on the adsorption characteristic of heavy metal ions (Ni^2+and Fe^3+) using a novel biosorbent, prepared from cell walls of Rhizopus oryzae. The optimum operating conditions are investigated in both...This paper reports on the adsorption characteristic of heavy metal ions (Ni^2+and Fe^3+) using a novel biosorbent, prepared from cell walls of Rhizopus oryzae. The optimum operating conditions are investigated in both single ion system and binary system.展开更多
N-wells are created by P＋ ion implantation into Si-faced p-type 4H-SiC epilayer. Ti and Ni are deposited in sequence on the surface of the active regions. Ni2Si is identified as the dominant phase by X-ray diffracti...N-wells are created by P＋ ion implantation into Si-faced p-type 4H-SiC epilayer. Ti and Ni are deposited in sequence on the surface of the active regions. Ni2Si is identified as the dominant phase by X-ray diffraction （XRD） analysis after metallization annealing. An amorphous C film at the Ni2 Si/SiC interface is confirmed by an X-ray energy-dispersive spectrometer （XEDS）. The Ni2Si and amorphous C film are etched away selectively,followed by deposition of new metal films without annealing. Measurement of the current-voltage characteristics shows that the contacts are still ohmic after the Ni2 Si and amorphous C film are replaced by new metal films. The sheet resistance Rsh of the implanted layers decreases from 975 to 438f2/D, because carbon vacancies （Vc） appeared during annealing,which act as donors for electrons in SiC.展开更多
Zn plays an important role in the protection of iron and steel from corrosion in sea water, and the alloying of Zn and Ni can improve its corrosion resistance. The corrosion behavior of Zn？Ni alloys in synthetic sea ...Zn plays an important role in the protection of iron and steel from corrosion in sea water, and the alloying of Zn and Ni can improve its corrosion resistance. The corrosion behavior of Zn？Ni alloys in synthetic sea water （3.5% NaCl, mass fraction） was studied using Tafel plot and electrochemical impedance spectroscopy （EIS） techniques. The corrosion resistance of the investigated alloys with various Ni contents （0.5%？10%, mass fraction） was compared with that of Zn. The results show that the corrosion resistance of Zn？Ni alloys （except 0.5% Ni） is superior to that of Zn. The 10% Ni gives the highest corrosion resistance due to the formation ofγ-Zn3Ni withγ-ZnNi phases in the alloy. In the case of alloy I （0.5% Ni）, it exhibits a higher corrosion rate （less corrosion resistance） than Zn.展开更多
Isooctane is a promising gasoline additive that could be produced by dimerization of isobutene(IB) with subsequent hydrogenation.In this work,the dimerization of IB has been carried out in a batch reactor over a tempe...Isooctane is a promising gasoline additive that could be produced by dimerization of isobutene(IB) with subsequent hydrogenation.In this work,the dimerization of IB has been carried out in a batch reactor over a temperature range of 338-383 K in the presence of laboratory prepared Ni/Al_2O_3 as a catalyst and n-pentane as solvent.The influence of various parameters such as temperature,catalyst loading and initial concentration of IB was examined.A Langmuir-Hinshelwood kinetic model of IB dimerization was established and the parameters were estimated on the basis of the measured data.The feasibility of oligomerization of IB based on the reactive distillation was simulated in ASPEN PLUS using the kinetics developed.The simulation results showed that the catalyst of Ni/Al_2O_3 had higher selectivity to diisobutene(DIB) and slightly lower conversion of IB than ion exchange resin in the absence of polar substances.展开更多
The graphene oxides （GOs） have attracted multidisciplinary study because of their special physicochemical properties. The high surface area and large amounts of oxygen-containing functional groups make GOs suitable ...The graphene oxides （GOs） have attracted multidisciplinary study because of their special physicochemical properties. The high surface area and large amounts of oxygen-containing functional groups make GOs suitable materials for the efficient elimination of heavy metal ions from aqueous solutions. Herein the sorption of Ni（Ⅱ） on GOs was studied using batch experi- ments, and the results showed that the sorption of Ni（Ⅱ） is strongly dependent on pH and ionic strength at pH〈8, and inde- pendent of ionic strength at pH〉8. The sorption of Ni（Ⅱ） is mainly dominated by outer-sphere surface complexation and ion exchange at low pH, and by inner-sphere surface complexation at high pH. The interaction of Ni（Ⅱ） with GOs was also inves- tigated by theoretical density functional theory （DFT） calculations, and the results show that the sorption of Ni（Ⅱ） on GOs is mainly attributed to the -COH and -COC groups and the DFT calculations show that Ni（Ⅱ） forms stable GO_Ni_triplet struc- ture with the binding energy of -39.44 kcal/mol, which is in good agreement with the batch sorption experimental results. The results are important for the application of GOs as adsorbents in the efficient removal of Ni（Ⅱ） from wastewater in environ- mental pollution cleanup.展开更多
The sorption behavior and microscopic sequestration mechanisms of radionuclide 63Ni（II） on mordenite as a function of aging time, ionic srength, initial 63Ni（II） concentrations, solid content and coexistent electr...The sorption behavior and microscopic sequestration mechanisms of radionuclide 63Ni（II） on mordenite as a function of aging time, ionic srength, initial 63Ni（II） concentrations, solid content and coexistent electrolyte ions were investigated by the combination of batch and EXAFS techniques. Macroscopic experiment results show that the sorption of 63Ni（II） is dependent on ionic strength at pH〈7, and independent of ionic strength at pH〉7. The sorption percentage of 63Ni（II） on mordenite increases with increasing solid content, while the sorption capacity decreases as solid content increases. The presence of different electrolyte ions can enhance or inhibit the sorption of Ni（II） on mordenite in various degrees. EXAFS analysis results of the sam- ples under three different ionic strengths suggest that the retained 63Ni（II） in these samples exists in an octahedral environment with six water ligands. In the initial period of rapid uptake, the sorption of 63Ni（II） is dominated by the formation of innersphere surface complexes. As aging time increases, 63Ni（II） sequestration behavior tends to be mainly controlled by the formation of Ni phyllosilicate coprecipitates and/or Ni（OH）2（s） precipitates. Results for the second shell fit of the sample prepared at an initial 63Ni（II） concentration of 100 mg/L indicate the possible formation of Ni polynuclear surface complexes. Both the macroscopic sorption data and the molecular level evidence of 63Ni（II） surface speciation at the mordenite/water interfaces should be factored into better predictions of the mobility and bioavailability of 63Ni（II） in environment mediums.展开更多
We suggest that a family of Ni-based compounds, which contain [Ni_2M_2O]~2à(M = chalcogen) layers with an antiperovskite structure constructed by mixed-anion Ni complexes, Ni M_4O_2, can be potential high tempera...We suggest that a family of Ni-based compounds, which contain [Ni_2M_2O]~2à(M = chalcogen) layers with an antiperovskite structure constructed by mixed-anion Ni complexes, Ni M_4O_2, can be potential high temperature superconductors(high-Tc) upon doping or applying pressure. The layer structures have been formed in many other transitional metal compounds such as La_2B_2Se_2O_3(B = Mn, Fe, Co). For the Ni-based compounds, we predict that the parental compounds host collinear antiferromagnetic states similar to those in iron-based high temperature superconductors. The electronic physics near Fermi energy is controlled by two egd-orbitals with completely independent in-plane kinematics. We predict that the superconductivity in this family is characterized by strong competition between extended s-wave and d-wave pairing symmetries.展开更多
Understanding the carbon-tolerant mechanisms from a microscopic view is of special importance to develop proper anodes for solid oxide fuel cells.In this work,we employed density-functional theory calculations to stud...Understanding the carbon-tolerant mechanisms from a microscopic view is of special importance to develop proper anodes for solid oxide fuel cells.In this work,we employed density-functional theory calculations to study the CH4 reaction mechanism over a Ni/TiO2 nanostructure,which experimentally demonstrated good carbon tolerance.Six potential pathways for methane reforming reactions were studied over the Ni/TiO2(110)surface under both dry and wet atmospheres,and the main concerns were focused on the impact of TiO2 and Ni/TiO2 interface on CO/H2 formation.Our calculations suggest that the reaction between carbon and the interfacial lattice oxygen to form CO*is the dominant pathway for CH4 reforming under both dry and wet atmospheres,and intervention of steam directly to oxidize C*with its dissociated OH*group is less favorable in energy than that to wipe off oxygen vacancy to get ready for next C*oxidation.In all investigated paths,desorption of CO*is one of the most difficult steps.Fortunately,CO*desorption can be greatly promoted by the large heat released from the previous CO*formation process under wet atmosphere.H2O adsorption and dissociation over the TiO2 surface are found to be much easier than those over Ni,yttria stabilized zirconia(YSZ)and CeO2,which should be the key reason for the greatly depressed carbon deposition over Ni-TiO2 particles than traditional YSZ-Ni and CeO2-Ni anode.Our study presents the detailed CO*formation mechanism in CH4 reforming process over the Ni/TiO2 surface,which will benefit future research for exploring new carbon-tolerant solid oxide fuel cell anodes.展开更多
文摘lmprovement of the charge separation of titanosilicate molecular sieves is critical to their use asphotocatalysts for oxidative organic transformations.In this work,MFI TS-1 molecular sievenanosheets(TS-1 NS)were synthesized by a low-temperature hydrothermal method using a tai-lored diquaternary ammonium surfactant as the structure-directing agent.Introducing Ni^2+cationsat the ion-exchange sites of the TS-1 NS framework significantly enhanced its photoactivity in aero-bic alcohol oxidation.The optimized Ni cation-functionalized TS-1 NS(Ni/TS-1 NS)provide impres-sive photoactivity,with a benzyl alcohol(BA)conversion of 78.9%and benzyl aldehyde(BAD)se-lectivity of 98.8%using O as the only oxidant under full light irradiation;this BAD yield is approx-imately six times greater than that obtained for bulk TS-1,and is maintained for five runs.The ex-cellent photoactivity of Ni/TS-1 NS is attributed to the significantly enlarged surface area of thetwo-dimensional morphology TS-1 NS,extra mesopores,and greatly improved charge separation.Compared with bulk TS-1,Ni/TS-1 NS has a much shorter charge transfer distance.Theas-introduced Ni species could capture the photoelectrons to further improve the charge separa-tion.This work opens the way to a class of highly selective,robust,and low-cost titanosilicate mo-lecular sieve-based photocatalysts with industrial potential for selective oxidative transformationsand pollutant degradation.
基金Supported by the National Nature Science Foundation of China
文摘This paper reports on the adsorption characteristic of heavy metal ions (Ni^2+and Fe^3+) using a novel biosorbent, prepared from cell walls of Rhizopus oryzae. The optimum operating conditions are investigated in both single ion system and binary system.
文摘N-wells are created by P＋ ion implantation into Si-faced p-type 4H-SiC epilayer. Ti and Ni are deposited in sequence on the surface of the active regions. Ni2Si is identified as the dominant phase by X-ray diffraction （XRD） analysis after metallization annealing. An amorphous C film at the Ni2 Si/SiC interface is confirmed by an X-ray energy-dispersive spectrometer （XEDS）. The Ni2Si and amorphous C film are etched away selectively,followed by deposition of new metal films without annealing. Measurement of the current-voltage characteristics shows that the contacts are still ohmic after the Ni2 Si and amorphous C film are replaced by new metal films. The sheet resistance Rsh of the implanted layers decreases from 975 to 438f2/D, because carbon vacancies （Vc） appeared during annealing,which act as donors for electrons in SiC.
文摘Zn plays an important role in the protection of iron and steel from corrosion in sea water, and the alloying of Zn and Ni can improve its corrosion resistance. The corrosion behavior of Zn？Ni alloys in synthetic sea water （3.5% NaCl, mass fraction） was studied using Tafel plot and electrochemical impedance spectroscopy （EIS） techniques. The corrosion resistance of the investigated alloys with various Ni contents （0.5%？10%, mass fraction） was compared with that of Zn. The results show that the corrosion resistance of Zn？Ni alloys （except 0.5% Ni） is superior to that of Zn. The 10% Ni gives the highest corrosion resistance due to the formation ofγ-Zn3Ni withγ-ZnNi phases in the alloy. In the case of alloy I （0.5% Ni）, it exhibits a higher corrosion rate （less corrosion resistance） than Zn.
基金Supported by the State key Development Program for Basic Research of China(2012CB720502)the National High Technology Research and Development(2012AA040306)+1 种基金the National Natural Science Foundation of China(21076074)the Shanghai Pujiang Talents Program(10PJ1402400)
文摘Isooctane is a promising gasoline additive that could be produced by dimerization of isobutene(IB) with subsequent hydrogenation.In this work,the dimerization of IB has been carried out in a batch reactor over a temperature range of 338-383 K in the presence of laboratory prepared Ni/Al_2O_3 as a catalyst and n-pentane as solvent.The influence of various parameters such as temperature,catalyst loading and initial concentration of IB was examined.A Langmuir-Hinshelwood kinetic model of IB dimerization was established and the parameters were estimated on the basis of the measured data.The feasibility of oligomerization of IB based on the reactive distillation was simulated in ASPEN PLUS using the kinetics developed.The simulation results showed that the catalyst of Ni/Al_2O_3 had higher selectivity to diisobutene(DIB) and slightly lower conversion of IB than ion exchange resin in the absence of polar substances.
基金supported by the Deanship of Scientific Research,King Abdulaziz University(41-130-36-Hi Ci)
文摘The graphene oxides （GOs） have attracted multidisciplinary study because of their special physicochemical properties. The high surface area and large amounts of oxygen-containing functional groups make GOs suitable materials for the efficient elimination of heavy metal ions from aqueous solutions. Herein the sorption of Ni（Ⅱ） on GOs was studied using batch experi- ments, and the results showed that the sorption of Ni（Ⅱ） is strongly dependent on pH and ionic strength at pH〈8, and inde- pendent of ionic strength at pH〉8. The sorption of Ni（Ⅱ） is mainly dominated by outer-sphere surface complexation and ion exchange at low pH, and by inner-sphere surface complexation at high pH. The interaction of Ni（Ⅱ） with GOs was also inves- tigated by theoretical density functional theory （DFT） calculations, and the results show that the sorption of Ni（Ⅱ） on GOs is mainly attributed to the -COH and -COC groups and the DFT calculations show that Ni（Ⅱ） forms stable GO_Ni_triplet struc- ture with the binding energy of -39.44 kcal/mol, which is in good agreement with the batch sorption experimental results. The results are important for the application of GOs as adsorbents in the efficient removal of Ni（Ⅱ） from wastewater in environ- mental pollution cleanup.
基金supported by the National Natural Science Foundation of China (20907055,20971126 & 21077107)the National Basic Research Program of China (2011CB933700)the Knowledge Innovation Program of CAS and Special Foundation for High-level Waste Disposal (2007-840)
文摘The sorption behavior and microscopic sequestration mechanisms of radionuclide 63Ni（II） on mordenite as a function of aging time, ionic srength, initial 63Ni（II） concentrations, solid content and coexistent electrolyte ions were investigated by the combination of batch and EXAFS techniques. Macroscopic experiment results show that the sorption of 63Ni（II） is dependent on ionic strength at pH〈7, and independent of ionic strength at pH〉7. The sorption percentage of 63Ni（II） on mordenite increases with increasing solid content, while the sorption capacity decreases as solid content increases. The presence of different electrolyte ions can enhance or inhibit the sorption of Ni（II） on mordenite in various degrees. EXAFS analysis results of the sam- ples under three different ionic strengths suggest that the retained 63Ni（II） in these samples exists in an octahedral environment with six water ligands. In the initial period of rapid uptake, the sorption of 63Ni（II） is dominated by the formation of innersphere surface complexes. As aging time increases, 63Ni（II） sequestration behavior tends to be mainly controlled by the formation of Ni phyllosilicate coprecipitates and/or Ni（OH）2（s） precipitates. Results for the second shell fit of the sample prepared at an initial 63Ni（II） concentration of 100 mg/L indicate the possible formation of Ni polynuclear surface complexes. Both the macroscopic sorption data and the molecular level evidence of 63Ni（II） surface speciation at the mordenite/water interfaces should be factored into better predictions of the mobility and bioavailability of 63Ni（II） in environment mediums.
基金supported by the Ministry of Science and Technology of China(2015CB921300 and 2017YFA0303100)the National Natural Science Foundation of China(1190020,11534014,and 11334012)+1 种基金the Strategic Priority Research Program of CAS(XDB07000000)the Key Research Program of the CAS(XDPB08-1)
文摘We suggest that a family of Ni-based compounds, which contain [Ni_2M_2O]~2à(M = chalcogen) layers with an antiperovskite structure constructed by mixed-anion Ni complexes, Ni M_4O_2, can be potential high temperature superconductors(high-Tc) upon doping or applying pressure. The layer structures have been formed in many other transitional metal compounds such as La_2B_2Se_2O_3(B = Mn, Fe, Co). For the Ni-based compounds, we predict that the parental compounds host collinear antiferromagnetic states similar to those in iron-based high temperature superconductors. The electronic physics near Fermi energy is controlled by two egd-orbitals with completely independent in-plane kinematics. We predict that the superconductivity in this family is characterized by strong competition between extended s-wave and d-wave pairing symmetries.
基金financially supported by the National Basic Research Program of China (2017YFA0402800 and 2016YFA0200602)the National Natural Science Foundation of China (51472228 and 21573204)+1 种基金the Fundamental Research Funds for the Central Universities (WK3430000004)the One Hundred Person Project of CAS
文摘Understanding the carbon-tolerant mechanisms from a microscopic view is of special importance to develop proper anodes for solid oxide fuel cells.In this work,we employed density-functional theory calculations to study the CH4 reaction mechanism over a Ni/TiO2 nanostructure,which experimentally demonstrated good carbon tolerance.Six potential pathways for methane reforming reactions were studied over the Ni/TiO2(110)surface under both dry and wet atmospheres,and the main concerns were focused on the impact of TiO2 and Ni/TiO2 interface on CO/H2 formation.Our calculations suggest that the reaction between carbon and the interfacial lattice oxygen to form CO*is the dominant pathway for CH4 reforming under both dry and wet atmospheres,and intervention of steam directly to oxidize C*with its dissociated OH*group is less favorable in energy than that to wipe off oxygen vacancy to get ready for next C*oxidation.In all investigated paths,desorption of CO*is one of the most difficult steps.Fortunately,CO*desorption can be greatly promoted by the large heat released from the previous CO*formation process under wet atmosphere.H2O adsorption and dissociation over the TiO2 surface are found to be much easier than those over Ni,yttria stabilized zirconia(YSZ)and CeO2,which should be the key reason for the greatly depressed carbon deposition over Ni-TiO2 particles than traditional YSZ-Ni and CeO2-Ni anode.Our study presents the detailed CO*formation mechanism in CH4 reforming process over the Ni/TiO2 surface,which will benefit future research for exploring new carbon-tolerant solid oxide fuel cell anodes.
