Dry reforming of methane(DRM)converts CH4 and CO_(2) to syngas.Photothermal DRM,which integrates temperature and light,is a sustainable method for storing solar energy in molecules.However,challenges such as limited l...Dry reforming of methane(DRM)converts CH4 and CO_(2) to syngas.Photothermal DRM,which integrates temperature and light,is a sustainable method for storing solar energy in molecules.However,challenges such as limited light absorption,low photocarrier separation efficiency,Ni sintering,and carbon deposition hinder DRM stability.Herein,we regulated Ni contents in(Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalysts to enhance the optical characteristics while addressing Ni sintering and carbon deposition issues.The(3Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst had insufficient Ni content,while the(9Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst showed excessive carbon deposition,leading to lower stability compared to the(6Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst,which achieved CH4 and CO_(2) rates to 231.0 μmol gcat^(-1)s^(-1) and 294.3 μmol gcat^(-1)s^(-1) ,respectively,at 973 K,with only 0.2 wt.%carbon deposition and no Ni sintering.This work adjusted Ni contents in(Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalysts to enhance DRM performance,which has implications for improving other reactions.展开更多
The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO_(2)reduction to CO,yet the chemical inertness of the metal cent...The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO_(2)reduction to CO,yet the chemical inertness of the metal center renders it to exhibit electrochemical activity only under high overpotentials.Herein,we report P-and S-doped Ni single-atom catalysts,i.e.symmetric Ni_(1)/PN_(4)and asymmetric Ni1/SN_(3)C can exhibit high catalytic activity of CO_(2)reduction with stable potential windows.It is revealed that the key intermediate*COOH in CO_(2)electroreduction is stabilized by heteroatom doping,which stems from the upward shift of the axial d_(z2)orbital of the active metal Ni atom.Furthermore,we investigate the potential-dependent free energetics and dynamic properties at the electrochemical interface on the Ni1/SN3C catalyst using ab initio molecular dynamics simulations with a full explicit solvent model.Based on the potential-dependent microkinetic model,we predict that S-atom doped Ni SAC shifts the onset potential of CO_(2)electroreduction from–0.88 to–0.80 V vs.RHE,exhibiting better activity.Overall,this work provides an in-depth understanding of structure-activity relationships and atomic-level electrochemical interfaces of catalytic systems,and offers insights into the rational design of heteroatom-doped catalysts for targeted catalysis.展开更多
Monolithic catalysts have been widely investigated for CO_(2) methanation due to their fast mass and heat transfer rate,but the effect of the interaction between the catalyst layer and the monolithic support has been ...Monolithic catalysts have been widely investigated for CO_(2) methanation due to their fast mass and heat transfer rate,but the effect of the interaction between the catalyst layer and the monolithic support has been little studied.In this work,Ni/Al_(2)O_(3)/SiC monolithic catalysts,Ni/Al_(2)O_(3) powder catalysts and Ni/Al_(2)O_(3)/SiC-M catalysts were prepared to explore the effect of Si-Al interaction between the catalyst layer and SiC ceramic for CO_(2) methanation performance.Ni/Al_(2)O_(3)/SiC exhibited a CO_(2) conversion of 53% and a CH_(4) specific reaction rate of 0.05 m mol·g^(-1)·s^(-1) under conditions of 0.1 M Pa,4 00℃,and a WHSV of 60000 ml·g^(-1)·h^(-1).The CO_(2) conversion raised by 0.15-fold and the CH_(4) specific reaction rate raised by 0.25-fold compared to Ni/Al_(2)O_(3) with the same catalyst content.SEM,XRD,Raman,and other characterization results revealed that the formation of Si-Al interaction between the catalyst layer and SiC ceramic could weaken the interaction between Ni and Al_(2)O_(3),thereby improving the catalytic activity of Ni/Al_(2)O_(3)/SiC catalyst.However,the Si-Al interaction was further strengthened during the hightemperature reaction process,which significantly weakened the interaction between Ni and Al_(2)O_(3),thereby leading to a decline in the catalytic performance of Ni/Al_(2)O_(3)/SiC catalyst during an 80-h stability test.This study provides valuable insights for future research and development of monolithic catalysts.展开更多
Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS a...Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS analyses and they were tested in partial oxidation of methane(CPO). The catalytic reaction was carried out at atmospheric pressure in a temperature range of 400–800℃ with a feed gas mixture containing methane and oxygen in a molecular ratio CH4/O2=2. The Ni catalyst exhibited 60% methane conversion with 60% selectivity to CO already at 500℃. On the contrary, the Ni–Ce catalyst was inert to CPO up to 700℃. Moreover, the former catalyst reproduced its activity at the descending temperatures maintaining a good stability at 600℃, over a reaction time of 80 h, whereas the latter one completely deactivated. Test of CH4 temperature programmed surface reaction(CH4-TPSR) revealed a higher methane activation temperature(> 100℃) for the Ni–Ce catalyst as compared to the Ni one. Noticeable improvement of the ceria containing catalyst occurred when the reaction test started at a temperature higher than the methane decomposition temperature. In this case, the sample achieved the same catalytic behavior of the Ni catalyst. As confirmed by XPS analyses, the distinct electronic state of the supported nickel was responsible for the differences in catalytic behavior.展开更多
Ni/Al_2O_3-SiO_2 catalysts were synthesized via one-step method employing SiO_2 as an additive for the selective hydrogenation of butyne-1,4-diol(B_3D) to butane-1,4-diol(B1D). The prepared catalysts were evaluated by...Ni/Al_2O_3-SiO_2 catalysts were synthesized via one-step method employing SiO_2 as an additive for the selective hydrogenation of butyne-1,4-diol(B_3D) to butane-1,4-diol(B1D). The prepared catalysts were evaluated by a series of characterization techniques including BET, XRD, SEM, EDX-mapping, TEM, H_2-TPR, XPS, NH_3-TPD and Py-FTIR. Compared to Ni/Al_2O_3 catalyst, the SiO_2-doped samples exhibited better B_3D conversion. SiO_2 could help to form a strong interaction between NiO with the support, which inhibited Ni agglomeration at high temperature, improved the Ni dispersion, and enhanced the hydrogenation activity. B_1D selectivity was mainly influenced by the quantity of Lewis acid sites in addition to the Ni dispersion. The catalyst with a silica loading of 6.4% demonstrated an excellent selectivity of 75.18%(by 13% higher than the contrastive Ni/Al_2O_3 catalyst), which was attributed to the larger amount of Lewis acid sites and the moderate interaction between NiO with the support, which could facilitate the nickel dispersion on a preferable surface area of 176.3 m^2/g of support.展开更多
EHMO calculations and orbital analysis of fragments were performed for the Synthetic reactions of oxygenates in Fischer-Tropsch synthesis using a butterfly model for four different metals (Nim Ru, Rh, Pd)supported on ...EHMO calculations and orbital analysis of fragments were performed for the Synthetic reactions of oxygenates in Fischer-Tropsch synthesis using a butterfly model for four different metals (Nim Ru, Rh, Pd)supported on SiO2 as catalysts. Four processest CO dissociation, coupling of CO and H to produce CHO.insertion of CO to M-CH3; insertion of CH2 to M-CH3 have been calculated. We compared the degree of CO bond activation and the banters of the foregoing processes for these four catalysts, it can be shown that Ni/SiO2 is a methanation catalyst, Ru/SiO2 and Rh/SiO2 can produce C2-oxygenated compound (acetaldehyde), especially Rh/SiO2 is a good catalyst for producing it, and Pd/SiO2 is a methanol Synthesis catalyst.展开更多
The effects of ethanol vapor pretreatment on the performance of CrOx/SiO2 catalysts during the dehydrogenation of propane to propylene were studied with and without the presence of CO2.The catalyst pretreated with eth...The effects of ethanol vapor pretreatment on the performance of CrOx/SiO2 catalysts during the dehydrogenation of propane to propylene were studied with and without the presence of CO2.The catalyst pretreated with ethanol vapor exhibited better catalytic activity than the pristine CrOx/SiO2,generating 41.4% propane conversion and 84.8% propylene selectivity.The various catalyst samples prepared were characterized by X-ray diffraction,transmission electron microscopy,temperature-programmed reduction,X-ray photoelectron spectroscopy and reflectance UV-Vis spectroscopy.The data show that coordinative Cr^3＋ species represent the active sites during the dehydrogenation of propane and that these species serve as precursors for the generation of Cr^3＋.Cr^3＋ is reduced during the reaction,leading to a decrease in catalytic activity.Following ethanol vapor pretreatment,the reduced CrOx in the catalyst is readily re-oxidized to Cr^6＋ by CO2.The pretreated catalyst thus exhibits high activity during the propane dehydrogenation reaction by maintaining the active Cr^3＋ states.展开更多
Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried ...Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried out over coral reef-like Ni/Al2O3 catalysts in a continuous flow type fixed-bed reactor.The structure and properties of the fresh and used catalysts were studied by SEM,N2 adsorption-desorption,XRD,H2-TPR,O2-TPO,TG and ICP-AES techniques.The results showed that the coral reef-like Ni/Al2O3 catalysts exhibited better activity than the conventional Ni/Al2O3-H2O catalysts.The activities of coral reef-like catalysts were in the order of Ni/Al2O3-673Ni/Al2O3-573Ni/Al2O3- 473Ni/Al2O3-773.Ni/Al2O3-673-EG catalyst showed not only good activity and improved stability but also superior resistance to carbon deposition,sintering,and Ni loss.Under the reaction conditions of CO/H2（molar ratio）=1：3,593 K,atmospheric pressure and a GHSV of 2500 h-1,CH4 selectivity was 84.7%,and the CO conversion reached 98.2%.展开更多
The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/TiO2 catalysts prepared by a liquid-phase chemical reduction method. The catalysts were characterized by inductively coupled plasm...The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/TiO2 catalysts prepared by a liquid-phase chemical reduction method. The catalysts were characterized by inductively coupled plasma (ICP), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and temperature-programmed reduction (TPR). Results show that the titania structure has favorable influence on physio-chemical and catalytic properties of Ni/TiO2 catalysts. Compared to commercial Raney nickel, the catalytic activity of Ni/TiO2 catalyst is much superior, irrespective of the titania structure. The catalytic activity of anatase titania supported nickel catalyst Ni/TiO2(A) is higher than that of rutile titania supported nickel catalyst Ni/TiO2(R), possibly because the reduction of nickel oxide to metallic nickel for Ni/TiO2(A) is easier than that for Ni/TiO2(R) at similar reaction conditions.展开更多
The deactivation of Ni/SiO2-Al2 O3 catalyst in hydrogenation of crude 1,4-butanediol was investigated.During the operation time of 2140 h,the catalyst showed slow activity decay.Characterization results,for four spent...The deactivation of Ni/SiO2-Al2 O3 catalyst in hydrogenation of crude 1,4-butanediol was investigated.During the operation time of 2140 h,the catalyst showed slow activity decay.Characterization results,for four spent catalysts used at different time,indicated that the main reason of the catalyst deactivation was the deposition of carbonaceous species that covered the active Ni and blocked mesopores of the catalyst.The TPO and SEM measurements revealed that the carbonaceous species included both oligomeric and polymeric species with high C/H ratio and showed sheet.Such carbonaceous species might be eliminated through either direct H2 reduction or the combined oxidation-reduction methodologies.展开更多
The deposition of NH4 HSO4 and the poisoning effect of SO2 on SCR catalyst are the main obstacles that restrict the industrial application of CeO2-doped SCR catalysts.In this work,deposited NH4 HSO4 decomposition beha...The deposition of NH4 HSO4 and the poisoning effect of SO2 on SCR catalyst are the main obstacles that restrict the industrial application of CeO2-doped SCR catalysts.In this work,deposited NH4 HSO4 decomposition behavior and SO2 poisoning over V2 O5-MoO3/TiO2 catalysts modified with CeO2 and SiO2 were investigated.By the means of characterization analysis,it was found that the addition of SiO2 into VMo/Ti-Ce had an impact on the interaction existed between catalyst surface atoms and NH4 HSO4.Temperatureprogrammed methods and in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)experiments indicated that the doping of SiO2 promoted the decomposition of deposited NH4 HSO4 on VMo/Ti-Ce catalyst surface by reducing the thermal stability of NH4 HSO4 and enhancing the NH4 HSO4 reactivity with NO in low temperature.And this improvement may be the reason for the better catalytic activity than VMo/Ti-Ce in the case of NH4 HSO4 deposition.Accompanied with cerium sulfate species generated over catalyst surface,the conversion of SO2 to SO3 was inhibited in SiCe mixed catalyst.The addition of SiO2 could promote the decomposition of cerium sulfate,which may be a potential strategy to enhance the resistance of SO2 poisoning over CeO2-modifed catalysts.展开更多
A 20 wt% Ni/bentonite catalyst was prepared by a solution combustion synthesis (SCS), which exhibited higher activity for the CO_2methanation than that of an impregnation method (IPM), and the catalyst prepared by SCS...A 20 wt% Ni/bentonite catalyst was prepared by a solution combustion synthesis (SCS), which exhibited higher activity for the CO_2methanation than that of an impregnation method (IPM), and the catalyst prepared by SCS showed a CO_2 conversion of 85% and a CH4selectivity of 100% at 300 °C, atmospheric pressure, and 3600 ml·(g cat)-1·h-1, and the catalyst exhibited stable within a 110-h reaction. The results showed higher me- tallic Ni dispersion, smaller Ni particle size, larger specific surface area and lower reduction temperature in the Ni/ bentonite prepared by SCS than that of IPM. And the Ni/bentonite prepared by the SCS moderated the interaction between NiO and bentonite.展开更多
The influence of calcination temperature on the structure and catalytic behavior of Ni/TiO2-SiO2 catalyst, for CO2 reforming of methane to synthesis gas under atmospheric pressure, was investigated. The results showed...The influence of calcination temperature on the structure and catalytic behavior of Ni/TiO2-SiO2 catalyst, for CO2 reforming of methane to synthesis gas under atmospheric pressure, was investigated. The results showed that the Ni/TiO2-SiO2 catalyst calcined at 700 ℃ had high and stable activity while the catalysts calcined at 550 and 850 ℃ had low and unstable activity. Depending on the calcination temperature, one, two, or three of the following Ni-containing species, NiO, Ni2.44Ti0.72Si0.07O4, and NiTiO3 were identified by combining the temperature programmed reduction （TPR） and X-ray diffraction （XRD） results. Their reducibility decreased in the sequence： NiO〉Ni2.44Ti0.72Si0.07O4〉NiTiO3. It suggests that high and stable activities observed over the Ni/TiO2-SiO2 catalyst calcined at 700 ~C were induced by the formation of Ni2.44Ti0.72Si0.07O4 and smaller NiO species crystallite size.展开更多
The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/Al2O3 catalyst on alumina support with different particle size. It is found that support particle size has significant influences ...The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/Al2O3 catalyst on alumina support with different particle size. It is found that support particle size has significant influences on physiochemical properties and catalytic activity of the resulting Ni/Al2O3 catalyst, but little influence on the selec-tivity. At a comparable amount of Ni loading, the catalytic activity of Ni/Al2O3 prepared with alumina support of smaller particle size is lower. The reduction behavior of the catalyst is a key factor in determining the catalytic activity of Ni/Al2O3 catalyst. The supported nickel catalyst 10.3Ni/Al2O3-3 improves the life span of the membrane by reducing fouling on the membrane surface compared to nano-sized nickel.展开更多
The CO2reforming of CH4is studied over MgO‐promoted Ni catalysts,which were supported on alumina prepared from hydrotalcite.This presents an improved stability compared with non‐promoted catalysts.The introduction o...The CO2reforming of CH4is studied over MgO‐promoted Ni catalysts,which were supported on alumina prepared from hydrotalcite.This presents an improved stability compared with non‐promoted catalysts.The introduction of the MgO promoter was achieved through the‘‘memory effect’’of the Ni‐Al hydrotalcite structure,and ICP‐MS confirmed that only0.42wt.%of Mg2+ions were added into the Ni‐Mg/Al catalyst.Although no differences in the Ni particle size and basicity strength were observed,the Ni‐Mg/Al catalyst showed a higher catalytic stability than the Ni/Al catalyst.A series of surface reaction experiments were used and showed that the addition of a MgO promoter with low concentration can promote CO2dissociation to form active surface oxygen arising from the formation of the Ni‐MgO interface sites.Therefore,the carbon‐resistance promotion by nature was suggested to contribute to an oxidative environment around Ni particles,which would increase the conversion of carbon residues from CH4cracking to yield CO on the Ni metal surface.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
Characteristics of carbon deposition of CH 4 and C 2H 4 decomposition over supported Ni and Ni Ce catalysts were studied by using a pulse reaction as well as BET, TPR, XPS and hydrogen chemisorption techniques. It...Characteristics of carbon deposition of CH 4 and C 2H 4 decomposition over supported Ni and Ni Ce catalysts were studied by using a pulse reaction as well as BET, TPR, XPS and hydrogen chemisorption techniques. It is found that there is a metal semiconductor interaction (MScI) in the Ni Ce catalyst, and the effect of MScI on the carbon deposition of CH 4 decomposition is opposite to that of C 2H 4. A novel model of carbon deposition of CH 4 or C 2H 4 decomposition was proposed.展开更多
Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central is...Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central issue.The development of fully renewable catalytic systems with easier metal recovery strategies would promote the viability and sustainability of synthetic natural gas production circular routes.Taking Ni and NiFe catalysts supported over g-Al_(2)O_(3) oxide as reference materials,this work evaluates the potentiality of Ni and NiFe supported biochar catalysts for CO_(2) methanation.The development of competitive biochar catalysts was found dependent on the creation of basic sites on the catalyst surface.Displaying lower Turn Over Frequencies than Ni/Al catalyst,the absence of basic sites achieved over Ni/C catalyst was related to the depleted catalyst performances.For NiFe catalysts,analogous Ni_(5)Fe_(1) alloys were constituted over both alumina and biochar supports.The highest specific activity of the catalyst series,exhibited by the NiFe/C catalyst,was related to the development of surface basic sites along with weaker NiFe-C interactions,which resulted in increased Ni0:NiO surface populations under reaction conditions.In summary,the present work establishes biochar supports as a competitive material to consider within the future low-carbon energetic panorama.展开更多
In this study, Ni/YZrOcatalysts prepared with impregnation method and treated by dielectric barrier discharge plasma(DBD) in different atmospheres have been investigated for methane dry reforming. It is revealed by H-...In this study, Ni/YZrOcatalysts prepared with impregnation method and treated by dielectric barrier discharge plasma(DBD) in different atmospheres have been investigated for methane dry reforming. It is revealed by H-TPR that plasma treatment can enhance the interaction between Ni O/Ni particles and the YZrOpyrochlore support. Therefore, catalysts with smaller Ni O and Ni grains sizes, higher metallic Ni active surface areas can be achieved, as evidenced by XRD, TEM and Hadsorption-desorption measurements. As a consequence, the plasma-treated catalysts show significantly improved activity, stability and coke resistance, as testified by the TEM and TGA-DSC results. Plasma treatment in H/Ar gas mixture is found to be the best condition to prepare Ni/YZrO, which can be used to obtain a catalyst with the highest activity, stability and most potent coke resistance. It is believed that the smaller Ni grain size and higher metallic Ni active surface area induced by plasma treatment are the inherent reasons accounting for the promoted reaction performance of the Ni/YZrOpyrochlore catalysts.展开更多
基金support from the National Natural Science Foundation of China(22078134)State Key Laboratory of Clean and Efficient Coal Utilization of Taiyuan University of Technology(SKL2022006)Natural Science Foundation of Chongqing(CSTB2023NSCQ-MSX0162)are greatly appreciated for the work.
文摘Dry reforming of methane(DRM)converts CH4 and CO_(2) to syngas.Photothermal DRM,which integrates temperature and light,is a sustainable method for storing solar energy in molecules.However,challenges such as limited light absorption,low photocarrier separation efficiency,Ni sintering,and carbon deposition hinder DRM stability.Herein,we regulated Ni contents in(Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalysts to enhance the optical characteristics while addressing Ni sintering and carbon deposition issues.The(3Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst had insufficient Ni content,while the(9Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst showed excessive carbon deposition,leading to lower stability compared to the(6Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst,which achieved CH4 and CO_(2) rates to 231.0 μmol gcat^(-1)s^(-1) and 294.3 μmol gcat^(-1)s^(-1) ,respectively,at 973 K,with only 0.2 wt.%carbon deposition and no Ni sintering.This work adjusted Ni contents in(Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalysts to enhance DRM performance,which has implications for improving other reactions.
文摘The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO_(2)reduction to CO,yet the chemical inertness of the metal center renders it to exhibit electrochemical activity only under high overpotentials.Herein,we report P-and S-doped Ni single-atom catalysts,i.e.symmetric Ni_(1)/PN_(4)and asymmetric Ni1/SN_(3)C can exhibit high catalytic activity of CO_(2)reduction with stable potential windows.It is revealed that the key intermediate*COOH in CO_(2)electroreduction is stabilized by heteroatom doping,which stems from the upward shift of the axial d_(z2)orbital of the active metal Ni atom.Furthermore,we investigate the potential-dependent free energetics and dynamic properties at the electrochemical interface on the Ni1/SN3C catalyst using ab initio molecular dynamics simulations with a full explicit solvent model.Based on the potential-dependent microkinetic model,we predict that S-atom doped Ni SAC shifts the onset potential of CO_(2)electroreduction from–0.88 to–0.80 V vs.RHE,exhibiting better activity.Overall,this work provides an in-depth understanding of structure-activity relationships and atomic-level electrochemical interfaces of catalytic systems,and offers insights into the rational design of heteroatom-doped catalysts for targeted catalysis.
基金the National Natural Science Foundation of China (22325804 and 22308148)the Natural Science Foundation of Jiangsu Province (BK20230344)the Natural Science Research Project of Jiangsu University (22KJB610001)。
文摘Monolithic catalysts have been widely investigated for CO_(2) methanation due to their fast mass and heat transfer rate,but the effect of the interaction between the catalyst layer and the monolithic support has been little studied.In this work,Ni/Al_(2)O_(3)/SiC monolithic catalysts,Ni/Al_(2)O_(3) powder catalysts and Ni/Al_(2)O_(3)/SiC-M catalysts were prepared to explore the effect of Si-Al interaction between the catalyst layer and SiC ceramic for CO_(2) methanation performance.Ni/Al_(2)O_(3)/SiC exhibited a CO_(2) conversion of 53% and a CH_(4) specific reaction rate of 0.05 m mol·g^(-1)·s^(-1) under conditions of 0.1 M Pa,4 00℃,and a WHSV of 60000 ml·g^(-1)·h^(-1).The CO_(2) conversion raised by 0.15-fold and the CH_(4) specific reaction rate raised by 0.25-fold compared to Ni/Al_(2)O_(3) with the same catalyst content.SEM,XRD,Raman,and other characterization results revealed that the formation of Si-Al interaction between the catalyst layer and SiC ceramic could weaken the interaction between Ni and Al_(2)O_(3),thereby improving the catalytic activity of Ni/Al_(2)O_(3)/SiC catalyst.However,the Si-Al interaction was further strengthened during the hightemperature reaction process,which significantly weakened the interaction between Ni and Al_(2)O_(3),thereby leading to a decline in the catalytic performance of Ni/Al_(2)O_(3)/SiC catalyst during an 80-h stability test.This study provides valuable insights for future research and development of monolithic catalysts.
基金The Executive Programme for Cooperation between Italy and India (Prot.No.MAE01054762017)。
文摘Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS analyses and they were tested in partial oxidation of methane(CPO). The catalytic reaction was carried out at atmospheric pressure in a temperature range of 400–800℃ with a feed gas mixture containing methane and oxygen in a molecular ratio CH4/O2=2. The Ni catalyst exhibited 60% methane conversion with 60% selectivity to CO already at 500℃. On the contrary, the Ni–Ce catalyst was inert to CPO up to 700℃. Moreover, the former catalyst reproduced its activity at the descending temperatures maintaining a good stability at 600℃, over a reaction time of 80 h, whereas the latter one completely deactivated. Test of CH4 temperature programmed surface reaction(CH4-TPSR) revealed a higher methane activation temperature(> 100℃) for the Ni–Ce catalyst as compared to the Ni one. Noticeable improvement of the ceria containing catalyst occurred when the reaction test started at a temperature higher than the methane decomposition temperature. In this case, the sample achieved the same catalytic behavior of the Ni catalyst. As confirmed by XPS analyses, the distinct electronic state of the supported nickel was responsible for the differences in catalytic behavior.
基金Financial support from the National Natural Science Foundation of China (21163019) is gratefully acknowledged
文摘Ni/Al_2O_3-SiO_2 catalysts were synthesized via one-step method employing SiO_2 as an additive for the selective hydrogenation of butyne-1,4-diol(B_3D) to butane-1,4-diol(B1D). The prepared catalysts were evaluated by a series of characterization techniques including BET, XRD, SEM, EDX-mapping, TEM, H_2-TPR, XPS, NH_3-TPD and Py-FTIR. Compared to Ni/Al_2O_3 catalyst, the SiO_2-doped samples exhibited better B_3D conversion. SiO_2 could help to form a strong interaction between NiO with the support, which inhibited Ni agglomeration at high temperature, improved the Ni dispersion, and enhanced the hydrogenation activity. B_1D selectivity was mainly influenced by the quantity of Lewis acid sites in addition to the Ni dispersion. The catalyst with a silica loading of 6.4% demonstrated an excellent selectivity of 75.18%(by 13% higher than the contrastive Ni/Al_2O_3 catalyst), which was attributed to the larger amount of Lewis acid sites and the moderate interaction between NiO with the support, which could facilitate the nickel dispersion on a preferable surface area of 176.3 m^2/g of support.
文摘EHMO calculations and orbital analysis of fragments were performed for the Synthetic reactions of oxygenates in Fischer-Tropsch synthesis using a butterfly model for four different metals (Nim Ru, Rh, Pd)supported on SiO2 as catalysts. Four processest CO dissociation, coupling of CO and H to produce CHO.insertion of CO to M-CH3; insertion of CH2 to M-CH3 have been calculated. We compared the degree of CO bond activation and the banters of the foregoing processes for these four catalysts, it can be shown that Ni/SiO2 is a methanation catalyst, Ru/SiO2 and Rh/SiO2 can produce C2-oxygenated compound (acetaldehyde), especially Rh/SiO2 is a good catalyst for producing it, and Pd/SiO2 is a methanol Synthesis catalyst.
基金the financial support from China Postdoctoral Science Foundation (2014M560224)
文摘The effects of ethanol vapor pretreatment on the performance of CrOx/SiO2 catalysts during the dehydrogenation of propane to propylene were studied with and without the presence of CO2.The catalyst pretreated with ethanol vapor exhibited better catalytic activity than the pristine CrOx/SiO2,generating 41.4% propane conversion and 84.8% propylene selectivity.The various catalyst samples prepared were characterized by X-ray diffraction,transmission electron microscopy,temperature-programmed reduction,X-ray photoelectron spectroscopy and reflectance UV-Vis spectroscopy.The data show that coordinative Cr^3＋ species represent the active sites during the dehydrogenation of propane and that these species serve as precursors for the generation of Cr^3＋.Cr^3＋ is reduced during the reaction,leading to a decrease in catalytic activity.Following ethanol vapor pretreatment,the reduced CrOx in the catalyst is readily re-oxidized to Cr^6＋ by CO2.The pretreated catalyst thus exhibits high activity during the propane dehydrogenation reaction by maintaining the active Cr^3＋ states.
基金financially supported by Independent Research Subject from Ministry of Science and Technology of China(No.2008BWZ005)
文摘Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried out over coral reef-like Ni/Al2O3 catalysts in a continuous flow type fixed-bed reactor.The structure and properties of the fresh and used catalysts were studied by SEM,N2 adsorption-desorption,XRD,H2-TPR,O2-TPO,TG and ICP-AES techniques.The results showed that the coral reef-like Ni/Al2O3 catalysts exhibited better activity than the conventional Ni/Al2O3-H2O catalysts.The activities of coral reef-like catalysts were in the order of Ni/Al2O3-673Ni/Al2O3-573Ni/Al2O3- 473Ni/Al2O3-773.Ni/Al2O3-673-EG catalyst showed not only good activity and improved stability but also superior resistance to carbon deposition,sintering,and Ni loss.Under the reaction conditions of CO/H2（molar ratio）=1：3,593 K,atmospheric pressure and a GHSV of 2500 h-1,CH4 selectivity was 84.7%,and the CO conversion reached 98.2%.
基金Supported by the National Basic Research Program (No.2003CB615702) and the National Natural Science Foundation of Chin(No.20436030).
文摘The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/TiO2 catalysts prepared by a liquid-phase chemical reduction method. The catalysts were characterized by inductively coupled plasma (ICP), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and temperature-programmed reduction (TPR). Results show that the titania structure has favorable influence on physio-chemical and catalytic properties of Ni/TiO2 catalysts. Compared to commercial Raney nickel, the catalytic activity of Ni/TiO2 catalyst is much superior, irrespective of the titania structure. The catalytic activity of anatase titania supported nickel catalyst Ni/TiO2(A) is higher than that of rutile titania supported nickel catalyst Ni/TiO2(R), possibly because the reduction of nickel oxide to metallic nickel for Ni/TiO2(A) is easier than that for Ni/TiO2(R) at similar reaction conditions.
基金Supported by the National Natural Science Foundation of China(21673132).
文摘The deactivation of Ni/SiO2-Al2 O3 catalyst in hydrogenation of crude 1,4-butanediol was investigated.During the operation time of 2140 h,the catalyst showed slow activity decay.Characterization results,for four spent catalysts used at different time,indicated that the main reason of the catalyst deactivation was the deposition of carbonaceous species that covered the active Ni and blocked mesopores of the catalyst.The TPO and SEM measurements revealed that the carbonaceous species included both oligomeric and polymeric species with high C/H ratio and showed sheet.Such carbonaceous species might be eliminated through either direct H2 reduction or the combined oxidation-reduction methodologies.
基金supported by the National Natural Science Foundation of China(No.51576039)
文摘The deposition of NH4 HSO4 and the poisoning effect of SO2 on SCR catalyst are the main obstacles that restrict the industrial application of CeO2-doped SCR catalysts.In this work,deposited NH4 HSO4 decomposition behavior and SO2 poisoning over V2 O5-MoO3/TiO2 catalysts modified with CeO2 and SiO2 were investigated.By the means of characterization analysis,it was found that the addition of SiO2 into VMo/Ti-Ce had an impact on the interaction existed between catalyst surface atoms and NH4 HSO4.Temperatureprogrammed methods and in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)experiments indicated that the doping of SiO2 promoted the decomposition of deposited NH4 HSO4 on VMo/Ti-Ce catalyst surface by reducing the thermal stability of NH4 HSO4 and enhancing the NH4 HSO4 reactivity with NO in low temperature.And this improvement may be the reason for the better catalytic activity than VMo/Ti-Ce in the case of NH4 HSO4 deposition.Accompanied with cerium sulfate species generated over catalyst surface,the conversion of SO2 to SO3 was inhibited in SiCe mixed catalyst.The addition of SiO2 could promote the decomposition of cerium sulfate,which may be a potential strategy to enhance the resistance of SO2 poisoning over CeO2-modifed catalysts.
基金Supported by the National Natural Science Foundation of China(21566005)the Natural Science Foundation of Guangxi Province(2016GXNSFFA380015)
文摘A 20 wt% Ni/bentonite catalyst was prepared by a solution combustion synthesis (SCS), which exhibited higher activity for the CO_2methanation than that of an impregnation method (IPM), and the catalyst prepared by SCS showed a CO_2 conversion of 85% and a CH4selectivity of 100% at 300 °C, atmospheric pressure, and 3600 ml·(g cat)-1·h-1, and the catalyst exhibited stable within a 110-h reaction. The results showed higher me- tallic Ni dispersion, smaller Ni particle size, larger specific surface area and lower reduction temperature in the Ni/ bentonite prepared by SCS than that of IPM. And the Ni/bentonite prepared by the SCS moderated the interaction between NiO and bentonite.
文摘The influence of calcination temperature on the structure and catalytic behavior of Ni/TiO2-SiO2 catalyst, for CO2 reforming of methane to synthesis gas under atmospheric pressure, was investigated. The results showed that the Ni/TiO2-SiO2 catalyst calcined at 700 ℃ had high and stable activity while the catalysts calcined at 550 and 850 ℃ had low and unstable activity. Depending on the calcination temperature, one, two, or three of the following Ni-containing species, NiO, Ni2.44Ti0.72Si0.07O4, and NiTiO3 were identified by combining the temperature programmed reduction （TPR） and X-ray diffraction （XRD） results. Their reducibility decreased in the sequence： NiO〉Ni2.44Ti0.72Si0.07O4〉NiTiO3. It suggests that high and stable activities observed over the Ni/TiO2-SiO2 catalyst calcined at 700 ~C were induced by the formation of Ni2.44Ti0.72Si0.07O4 and smaller NiO species crystallite size.
基金Supported by the Special Funds for Major State Basic Research Program of China （No.2003CB615702）, the National Natural Science Foundation of China （No.20636020） and the Natural Science Foundation of Jiangsu Province （No.BK2006722）.
文摘The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/Al2O3 catalyst on alumina support with different particle size. It is found that support particle size has significant influences on physiochemical properties and catalytic activity of the resulting Ni/Al2O3 catalyst, but little influence on the selec-tivity. At a comparable amount of Ni loading, the catalytic activity of Ni/Al2O3 prepared with alumina support of smaller particle size is lower. The reduction behavior of the catalyst is a key factor in determining the catalytic activity of Ni/Al2O3 catalyst. The supported nickel catalyst 10.3Ni/Al2O3-3 improves the life span of the membrane by reducing fouling on the membrane surface compared to nano-sized nickel.
基金supported by the National Natural Science Fundation of China(U1361202,51276120)~~
文摘The CO2reforming of CH4is studied over MgO‐promoted Ni catalysts,which were supported on alumina prepared from hydrotalcite.This presents an improved stability compared with non‐promoted catalysts.The introduction of the MgO promoter was achieved through the‘‘memory effect’’of the Ni‐Al hydrotalcite structure,and ICP‐MS confirmed that only0.42wt.%of Mg2+ions were added into the Ni‐Mg/Al catalyst.Although no differences in the Ni particle size and basicity strength were observed,the Ni‐Mg/Al catalyst showed a higher catalytic stability than the Ni/Al catalyst.A series of surface reaction experiments were used and showed that the addition of a MgO promoter with low concentration can promote CO2dissociation to form active surface oxygen arising from the formation of the Ni‐MgO interface sites.Therefore,the carbon‐resistance promotion by nature was suggested to contribute to an oxidative environment around Ni particles,which would increase the conversion of carbon residues from CH4cracking to yield CO on the Ni metal surface.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
文摘Characteristics of carbon deposition of CH 4 and C 2H 4 decomposition over supported Ni and Ni Ce catalysts were studied by using a pulse reaction as well as BET, TPR, XPS and hydrogen chemisorption techniques. It is found that there is a metal semiconductor interaction (MScI) in the Ni Ce catalyst, and the effect of MScI on the carbon deposition of CH 4 decomposition is opposite to that of C 2H 4. A novel model of carbon deposition of CH 4 or C 2H 4 decomposition was proposed.
文摘Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central issue.The development of fully renewable catalytic systems with easier metal recovery strategies would promote the viability and sustainability of synthetic natural gas production circular routes.Taking Ni and NiFe catalysts supported over g-Al_(2)O_(3) oxide as reference materials,this work evaluates the potentiality of Ni and NiFe supported biochar catalysts for CO_(2) methanation.The development of competitive biochar catalysts was found dependent on the creation of basic sites on the catalyst surface.Displaying lower Turn Over Frequencies than Ni/Al catalyst,the absence of basic sites achieved over Ni/C catalyst was related to the depleted catalyst performances.For NiFe catalysts,analogous Ni_(5)Fe_(1) alloys were constituted over both alumina and biochar supports.The highest specific activity of the catalyst series,exhibited by the NiFe/C catalyst,was related to the development of surface basic sites along with weaker NiFe-C interactions,which resulted in increased Ni0:NiO surface populations under reaction conditions.In summary,the present work establishes biochar supports as a competitive material to consider within the future low-carbon energetic panorama.
基金supported by the National Natural Science Foundation of China (21567016, 21566022, 21263015)the Natural Science Foundation of Jiangxi Province (20151BBE50006, 20151BAB203024)the Education Department of Jiangxi Province (KJLD14005, GJJ150016)
文摘In this study, Ni/YZrOcatalysts prepared with impregnation method and treated by dielectric barrier discharge plasma(DBD) in different atmospheres have been investigated for methane dry reforming. It is revealed by H-TPR that plasma treatment can enhance the interaction between Ni O/Ni particles and the YZrOpyrochlore support. Therefore, catalysts with smaller Ni O and Ni grains sizes, higher metallic Ni active surface areas can be achieved, as evidenced by XRD, TEM and Hadsorption-desorption measurements. As a consequence, the plasma-treated catalysts show significantly improved activity, stability and coke resistance, as testified by the TEM and TGA-DSC results. Plasma treatment in H/Ar gas mixture is found to be the best condition to prepare Ni/YZrO, which can be used to obtain a catalyst with the highest activity, stability and most potent coke resistance. It is believed that the smaller Ni grain size and higher metallic Ni active surface area induced by plasma treatment are the inherent reasons accounting for the promoted reaction performance of the Ni/YZrOpyrochlore catalysts.
