We applied periodic density-functional theory to investigate the adsorption of HCN on x Ni@Pt(111) bimetallic surfaces(x = 1~4). The results have been compared with those obtained on pure Ni(111) and Pt(111) s...We applied periodic density-functional theory to investigate the adsorption of HCN on x Ni@Pt(111) bimetallic surfaces(x = 1~4). The results have been compared with those obtained on pure Ni(111) and Pt(111) surfaces. For all bimetallic surfaces,HCN is preferentially tilted with the CN bond parallel to the surface,and adsorption energies increase with an increasing number of layer Ni atoms on the surface. The adsorption energies of HCN on all bimetallic surfaces are larger than that on the Pt(111) surface,whereas the adsorption energies of HCN on 3Ni@Pt(111) and 4Ni@Pt(111) are larger than that on the Ni(111) surface,indicating that the introduction of Ni to the Pt catalyst could increase the activity of bimetallic catalyst in the hydrogenation reaction for nitriles. Larger adsorption energy of HCN leads to a longer C–N bond length and a smaller CN vibrational frequency. The analysis of Bader charge and vibrational frequencies showed obvious weakening of the adsorbed C–N bond and an indication of sp2 hybridization of both carbon and nitrogen atoms.展开更多
Hydrotalcite precursors of La modified Ni-Al2O3 and Ni-SiO2 catalysts prepared by co-precipitation method and the catalytic activities were examined for the production of COx-free H2 by CH4 decomposition. Physico-chem...Hydrotalcite precursors of La modified Ni-Al2O3 and Ni-SiO2 catalysts prepared by co-precipitation method and the catalytic activities were examined for the production of COx-free H2 by CH4 decomposition. Physico-chemical characteristics of fresh, reduced and used catalysts were evaluated by XRD, TPR and O2 pulse chemisorptions, TEM and BET-SA techniques. XRD studies showed phases due to hydrotalcite-like precursors in oven dried form produced dispersed NiO species upon calcination in static air above 450 C. Raman spectra of deactivated samples revealed the presence of both ordered and disordered forms of carbon. Ni-La-Al2O3catalyst with a mole ratio of Ni : La : Al = 2 : 0.1 : 0.9 exhibited tremendously high longevity with a hydrogen production rate of 1300 molH2 mol 1 Ni. A direct relationship between Ni metal surface area and hydrogen yields was established.展开更多
The surface infiltrated composite (Ni/WC) layers on gray iron substrate were fabricated through a vacuum infiltration casting technique (VICT) using Ni-based composite powder with different WC particles content as...The surface infiltrated composite (Ni/WC) layers on gray iron substrate were fabricated through a vacuum infiltration casting technique (VICT) using Ni-based composite powder with different WC particles content as raw materials.The microstructures of surface infiltrated composite layer,the interface structures between surface composite layer and the substrate,the changes of macro-hardness with the increasing of WC content and the micro-hardness distribution are investigated.The infiltrated composite layer includes a surface composite layer and a transition layer,and the thickness of the transition layer decreases with the increasing content of WC.The thickness of transition layer with 20%WC content in the surface infiltrated composite layer was 170 μm which was the thickest for all transition layers with different WC content.The surface composite layer was mainly composed of WC,W2C,FeB and NiB,along with Ni-Cr-Fe,Ni (Cr) solid solution,Ni (Si) solid solution and Ni (Fe) solid solution.The transition layer was composed of Ni (Cr) solid solution,Ni (Fe) solid solution,Ni (Si) solid solution,Fe (Ni) solid solution and eutectic.The surface macro-hardness and micro-hardness of the infiltrated layer had been evaluated.The macro-hardness of the surface composite layer decreases with the WC content increasing,and the average macro-hardness is HRC60.The distribution of micro-hardness presents gradient change.The average micro-hardness of the infiltrated layer is about HV1000.展开更多
Highly active MCM-41 supported nickel phosphide catalysts for hydrodesulfurization (HDS) were synthesized by two different phosphorus sources, in which the surface of Ni2P catalysts were modified by air instead of b...Highly active MCM-41 supported nickel phosphide catalysts for hydrodesulfurization (HDS) were synthesized by two different phosphorus sources, in which the surface of Ni2P catalysts were modified by air instead of being passivated by O2/N2 mixture. In addition, the catalysts need not be activated with flowing H2 (30 ml·min^-1) at 500℃ for 2 h prior to reaction as traditional method. X-ray diffraction (XRD), X-ray photoelectro spectroscopy (XPS), N2-adsorption specific surface area measurements and CO chemisorption were used to characterize the resulting catalysts. The effect of modification with air on the surface of the catalysts for HDS performance was investigated. Results showed that the surface modification with air can promote the formation of smaller Ni2P particles and more active Ni sites on surface of catalysts. At 3.0 MPa and 613 K, the dibenzothiophene (DBT) conversion of the catalysts modified with air was 98.7%, which was 7.1% higher than that of catalyst passivated by O2/N2 mixture. The higher activities of Ni2P(x)/M41-O catalysts can be attributed to the smaller Ni2P particles sizes and the increased hydrogen dissociation activity due to the surface modification.展开更多
Adsorption-desorption kinetics of CO and H_2 on Ni surface were studied with molecular beam relaxation spectrometry. It is found that there are two adsorbed states in the substrate temperature range 330K<T<480K ...Adsorption-desorption kinetics of CO and H_2 on Ni surface were studied with molecular beam relaxation spectrometry. It is found that there are two adsorbed states in the substrate temperature range 330K<T<480K and 720K<T<900K respectively for CO/Ni system. These results can be explained by a precursor state model. Their kinetic parameters: E_(aα)=14.6kJ/mol, E_(dx)=49.3kJ/mol; E_(aβ)= 68.6kJ/mol, E_(dβ)=200.6kJ/mol. It is shown that there are two adsorbed states in the low (350K<T<430K) and high (550K<T<625K) temperature range respectively for H_2/Ni system. These results can be explained by a direct dissociative model. Their kinetic parameters:E_(dl)=26.3kJ/mol, E_(dh)=103.7kJ/mol.展开更多
The activated chemisorption of N<sub>2</sub> on Ni (poly) and La film was performed on a molecular beam—surface scattering apparatus. Experimental results indicate that the initial sticking probability ...The activated chemisorption of N<sub>2</sub> on Ni (poly) and La film was performed on a molecular beam—surface scattering apparatus. Experimental results indicate that the initial sticking probability s<sub>o</sub> increases linearly from 0 to 0.03 as normal component of translational energy of the molecuar beam E<sub>n</sub> increases from 11.00 to 19.91 kcal/mol for N<sub>2</sub>/Ni system and S<sub>0</sub> from 0 to 0. 10 as E<sub>n</sub> from 10. 40 to 19.91 kcal/mol for N<sub>2</sub>/La system. The apparent activation energy △E are 6.16 kcal/mol and 5.30 kcal/mol for N<sub>2</sub>/Ni and N<sub>2</sub>/La systems respectively.展开更多
The interaction of cyanide (CN) with different sites on Ni(111) surface is studied by using density functional theory (DFT). Ni19 cluster is used to simulate the surface. The present calculations show that the end-o...The interaction of cyanide (CN) with different sites on Ni(111) surface is studied by using density functional theory (DFT). Ni19 cluster is used to simulate the surface. The present calculations show that the end-on bonded (through C atom) configuration is much more preferable than the side-on bonded CN or other configurations on the same adsorption site. For all adsorption modes, adsorption energies at the top, bridge, and three-fold sites on Ni(111) are comparable, with the bridge site of the end-on bonded CN (through C atom) more favorable than other adsorption sites. CN vibrational frequencies are red-shifted at all cases, except that the end-on CN bonded (through C atom) on the top site is blue-shifted. The bonding of CN on the Ni(111) surface is large- ly ionic.展开更多
Investigation has been made into the causes of cracking in the Surfacing welding layer of Ni3Al based alloy by analysing both the liqu id-to-solid transformation in the molten pool and the distribution of thermal stre...Investigation has been made into the causes of cracking in the Surfacing welding layer of Ni3Al based alloy by analysing both the liqu id-to-solid transformation in the molten pool and the distribution of thermal stress within the surfacing welding layer. The results show that cracking in the surfacing welding layer is directly related to the producing of eutectic phase β' (NiAl) in the interdendritic region and high thermal stress within the surfacing welding layer. When the process of electric arc surfacing welding is changed from along straight line to along' Z' pattern, cracking in the surfacing welding layer of Ni3Al based alloy is prevented due to being reduced of both the cooling rate of liquid in the molten pool and the moving speed of the heat source. Reducing the melting volume of the substrate material by lowering the output power of electric arc welding would make the content of iron atoms in the molten pool decrease. and this also can reduce the trend of the eutectic reaction in the interdendfitic region and is helpful to Suppress cracking in the surfacing welding layer.展开更多
The influences of increasing the number of d-electrons in the single metal(Fe-like)substituted(111)n surface ofγ-Al2O3 on its possible catalytic effects were explored.The energetic properties,local structures,and in-...The influences of increasing the number of d-electrons in the single metal(Fe-like)substituted(111)n surface ofγ-Al2O3 on its possible catalytic effects were explored.The energetic properties,local structures,and in-site electron configurations of the most active tri-coordinated Co and Ni single-site(111)n surface ofγ-Al2O3 have been studied using the density functional theory(DFT)approach under periodic boundary conditions.The replacement of Al by a Co or Ni atom on the I position of the(111)n surface leads to significant elongations of metal–O distances.The energy released from the substitution process on the AlI site of the(111)n surface follows the sequence NiI(164.85 kcal mol−1)>CoI(113.17 kcal mol−1)>FeI(44.30 kcal mol−1).The triplet and quintet(ground state)of the CoI substituted complex are energy degenerate.Also,the doublet and quartet(ground state)of the NiI substituted complex have the same stable energy.This energy degeneracy comes from theα–βelectron flipping on the p-orbital of the neighboring O that is next to the substituted CoI or NiI site on the(111)n surface ofγ-Al2O3.Different from the FeI substituted single-site(111)n surface,in which the electron configuration of FeI varies according to its spin-multiplicity state,substituted NiI has a unique d8 electron configuration in all three spin states,and similarly,CoI has a unique d7 electron configuration in all three open shell spin states.An increase of the population of d-electrons in the single metal substituted(111)n surface ofγ-Al2O3 is likely to provide a more stable electron configuration in the metal catalytic center.展开更多
基金supported by the National Natural Science Foundation of China(21203027,21373048,21371034)Scientific Development Fund of Fuzhou University(2012-XQ-11)
文摘We applied periodic density-functional theory to investigate the adsorption of HCN on x Ni@Pt(111) bimetallic surfaces(x = 1~4). The results have been compared with those obtained on pure Ni(111) and Pt(111) surfaces. For all bimetallic surfaces,HCN is preferentially tilted with the CN bond parallel to the surface,and adsorption energies increase with an increasing number of layer Ni atoms on the surface. The adsorption energies of HCN on all bimetallic surfaces are larger than that on the Pt(111) surface,whereas the adsorption energies of HCN on 3Ni@Pt(111) and 4Ni@Pt(111) are larger than that on the Ni(111) surface,indicating that the introduction of Ni to the Pt catalyst could increase the activity of bimetallic catalyst in the hydrogenation reaction for nitriles. Larger adsorption energy of HCN leads to a longer C–N bond length and a smaller CN vibrational frequency. The analysis of Bader charge and vibrational frequencies showed obvious weakening of the adsorbed C–N bond and an indication of sp2 hybridization of both carbon and nitrogen atoms.
文摘Hydrotalcite precursors of La modified Ni-Al2O3 and Ni-SiO2 catalysts prepared by co-precipitation method and the catalytic activities were examined for the production of COx-free H2 by CH4 decomposition. Physico-chemical characteristics of fresh, reduced and used catalysts were evaluated by XRD, TPR and O2 pulse chemisorptions, TEM and BET-SA techniques. XRD studies showed phases due to hydrotalcite-like precursors in oven dried form produced dispersed NiO species upon calcination in static air above 450 C. Raman spectra of deactivated samples revealed the presence of both ordered and disordered forms of carbon. Ni-La-Al2O3catalyst with a mole ratio of Ni : La : Al = 2 : 0.1 : 0.9 exhibited tremendously high longevity with a hydrogen production rate of 1300 molH2 mol 1 Ni. A direct relationship between Ni metal surface area and hydrogen yields was established.
基金Funded by"Xi-Bu-Zhi-Guang" Foundation of Chinese Academy of Sciences(No.XBZG-2007-5)Gansu Natural Science Foundation of China(No.0806RJYA004)Outstanding Youngth of Lanzhou University of Technology (No.Q200910)
文摘The surface infiltrated composite (Ni/WC) layers on gray iron substrate were fabricated through a vacuum infiltration casting technique (VICT) using Ni-based composite powder with different WC particles content as raw materials.The microstructures of surface infiltrated composite layer,the interface structures between surface composite layer and the substrate,the changes of macro-hardness with the increasing of WC content and the micro-hardness distribution are investigated.The infiltrated composite layer includes a surface composite layer and a transition layer,and the thickness of the transition layer decreases with the increasing content of WC.The thickness of transition layer with 20%WC content in the surface infiltrated composite layer was 170 μm which was the thickest for all transition layers with different WC content.The surface composite layer was mainly composed of WC,W2C,FeB and NiB,along with Ni-Cr-Fe,Ni (Cr) solid solution,Ni (Si) solid solution and Ni (Fe) solid solution.The transition layer was composed of Ni (Cr) solid solution,Ni (Fe) solid solution,Ni (Si) solid solution,Fe (Ni) solid solution and eutectic.The surface macro-hardness and micro-hardness of the infiltrated layer had been evaluated.The macro-hardness of the surface composite layer decreases with the WC content increasing,and the average macro-hardness is HRC60.The distribution of micro-hardness presents gradient change.The average micro-hardness of the infiltrated layer is about HV1000.
基金Supported by the National Natural Science Foundation of China(21276048)the Project of Education Department of Heilongjiang Province,China(12541060)the Graduate Innovation Project of Northeast Petroleum University,China(YJSCX2016-019NEPU)
文摘Highly active MCM-41 supported nickel phosphide catalysts for hydrodesulfurization (HDS) were synthesized by two different phosphorus sources, in which the surface of Ni2P catalysts were modified by air instead of being passivated by O2/N2 mixture. In addition, the catalysts need not be activated with flowing H2 (30 ml·min^-1) at 500℃ for 2 h prior to reaction as traditional method. X-ray diffraction (XRD), X-ray photoelectro spectroscopy (XPS), N2-adsorption specific surface area measurements and CO chemisorption were used to characterize the resulting catalysts. The effect of modification with air on the surface of the catalysts for HDS performance was investigated. Results showed that the surface modification with air can promote the formation of smaller Ni2P particles and more active Ni sites on surface of catalysts. At 3.0 MPa and 613 K, the dibenzothiophene (DBT) conversion of the catalysts modified with air was 98.7%, which was 7.1% higher than that of catalyst passivated by O2/N2 mixture. The higher activities of Ni2P(x)/M41-O catalysts can be attributed to the smaller Ni2P particles sizes and the increased hydrogen dissociation activity due to the surface modification.
文摘Adsorption-desorption kinetics of CO and H_2 on Ni surface were studied with molecular beam relaxation spectrometry. It is found that there are two adsorbed states in the substrate temperature range 330K<T<480K and 720K<T<900K respectively for CO/Ni system. These results can be explained by a precursor state model. Their kinetic parameters: E_(aα)=14.6kJ/mol, E_(dx)=49.3kJ/mol; E_(aβ)= 68.6kJ/mol, E_(dβ)=200.6kJ/mol. It is shown that there are two adsorbed states in the low (350K<T<430K) and high (550K<T<625K) temperature range respectively for H_2/Ni system. These results can be explained by a direct dissociative model. Their kinetic parameters:E_(dl)=26.3kJ/mol, E_(dh)=103.7kJ/mol.
基金Project supportec by the National Natural Science Foundation of China
文摘The activated chemisorption of N<sub>2</sub> on Ni (poly) and La film was performed on a molecular beam—surface scattering apparatus. Experimental results indicate that the initial sticking probability s<sub>o</sub> increases linearly from 0 to 0.03 as normal component of translational energy of the molecuar beam E<sub>n</sub> increases from 11.00 to 19.91 kcal/mol for N<sub>2</sub>/Ni system and S<sub>0</sub> from 0 to 0. 10 as E<sub>n</sub> from 10. 40 to 19.91 kcal/mol for N<sub>2</sub>/La system. The apparent activation energy △E are 6.16 kcal/mol and 5.30 kcal/mol for N<sub>2</sub>/Ni and N<sub>2</sub>/La systems respectively.
基金This work was supported by the National Natural Science Foundation of China (20273013 20303002)+1 种基金 the Fujian Province Key Foundation (K02012) the State Key Laboratory of Structural Chemistry (020051) and Fuzhou University (2004XY04)
文摘The interaction of cyanide (CN) with different sites on Ni(111) surface is studied by using density functional theory (DFT). Ni19 cluster is used to simulate the surface. The present calculations show that the end-on bonded (through C atom) configuration is much more preferable than the side-on bonded CN or other configurations on the same adsorption site. For all adsorption modes, adsorption energies at the top, bridge, and three-fold sites on Ni(111) are comparable, with the bridge site of the end-on bonded CN (through C atom) more favorable than other adsorption sites. CN vibrational frequencies are red-shifted at all cases, except that the end-on CN bonded (through C atom) on the top site is blue-shifted. The bonding of CN on the Ni(111) surface is large- ly ionic.
文摘Investigation has been made into the causes of cracking in the Surfacing welding layer of Ni3Al based alloy by analysing both the liqu id-to-solid transformation in the molten pool and the distribution of thermal stress within the surfacing welding layer. The results show that cracking in the surfacing welding layer is directly related to the producing of eutectic phase β' (NiAl) in the interdendritic region and high thermal stress within the surfacing welding layer. When the process of electric arc surfacing welding is changed from along straight line to along' Z' pattern, cracking in the surfacing welding layer of Ni3Al based alloy is prevented due to being reduced of both the cooling rate of liquid in the molten pool and the moving speed of the heat source. Reducing the melting volume of the substrate material by lowering the output power of electric arc welding would make the content of iron atoms in the molten pool decrease. and this also can reduce the trend of the eutectic reaction in the interdendfitic region and is helpful to Suppress cracking in the surfacing welding layer.
基金supported by the NSF PREM grant#1826886The computer time was provided by the Extreme Science and Engineering Discovery Environment(XSEDE)by the National Science Foundation Grant Number OCI-1053575XSEDE award allocation number DMR110088 and by the Mississippi Center for Supercomputer Research.
文摘The influences of increasing the number of d-electrons in the single metal(Fe-like)substituted(111)n surface ofγ-Al2O3 on its possible catalytic effects were explored.The energetic properties,local structures,and in-site electron configurations of the most active tri-coordinated Co and Ni single-site(111)n surface ofγ-Al2O3 have been studied using the density functional theory(DFT)approach under periodic boundary conditions.The replacement of Al by a Co or Ni atom on the I position of the(111)n surface leads to significant elongations of metal–O distances.The energy released from the substitution process on the AlI site of the(111)n surface follows the sequence NiI(164.85 kcal mol−1)>CoI(113.17 kcal mol−1)>FeI(44.30 kcal mol−1).The triplet and quintet(ground state)of the CoI substituted complex are energy degenerate.Also,the doublet and quartet(ground state)of the NiI substituted complex have the same stable energy.This energy degeneracy comes from theα–βelectron flipping on the p-orbital of the neighboring O that is next to the substituted CoI or NiI site on the(111)n surface ofγ-Al2O3.Different from the FeI substituted single-site(111)n surface,in which the electron configuration of FeI varies according to its spin-multiplicity state,substituted NiI has a unique d8 electron configuration in all three spin states,and similarly,CoI has a unique d7 electron configuration in all three open shell spin states.An increase of the population of d-electrons in the single metal substituted(111)n surface ofγ-Al2O3 is likely to provide a more stable electron configuration in the metal catalytic center.