Recent research progress on the use of Ni-based catalysts supported by various carbon materials,such as carbon nanotubes,graphene,and activated carbon,for the hydrogenation of CO_(2)to CH4 is summarized.The influence ...Recent research progress on the use of Ni-based catalysts supported by various carbon materials,such as carbon nanotubes,graphene,and activated carbon,for the hydrogenation of CO_(2)to CH4 is summarized.The influence of additives and surface modification methods on improving their catalytic performance is discussed as is the reaction mechanism,especially the structurefunction relationship produced by the carbon.The review provides a comprehensive directory for the rational design of carbon-supported Ni-based catalysts for the methanation of CO_(2).展开更多
With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Ni...With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.展开更多
Photothermal catalytic methane dry reforming(DRM)technology can convert greenhouse gases(i.e.CH_(4)and CO_(2))into syngas(i.e.H_(2)and CO),providing more opportunities for reducing the greenhouse effect and achieving ...Photothermal catalytic methane dry reforming(DRM)technology can convert greenhouse gases(i.e.CH_(4)and CO_(2))into syngas(i.e.H_(2)and CO),providing more opportunities for reducing the greenhouse effect and achieving carbon neutrality.In the DRM field,Ni-based catalysts attract wide attention due to their low cost and high activity.However,the carbon deposition over Ni-based catalysts always leads to rapid deactivation,which is still a main challenge.To improve the long-term stability of Ni-based catalysts,this work proposes a carbon-atom-diffusion strategy under photothermal conditions and investigates its effect on a Zn-doped Ni-based photothermal catalyst(Ni_(3)Zn@CeO_(2)).The photothermal catalytic behavior of Ni_(3)Zn@CeO_(2)can maintain more than 70 h in DRM reaction.And the photocatalytic DRM activity of Ni_(3)Zn@CeO_(2)is 1.2 times higher than thermal catalytic activity.Density functional theory(DFT)calculation and experimental characterizations indicate that Ni_(3)Zn promotes the diffusion of carbon atoms into the Ni_(3)Zn to form the Ni_(3)ZnC0.7 phase with body-centered cubic(bcc)structure,thus inhibiting carbon deposition.Further,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy and DFT calculation prove Ni_(3)Zn@CeO_(2)benefits the CH_(4)activation and inhibits the carbon deposition during the DRM process.Through inducing carbon atoms diffusion within the Ni_(3)Zn lattice,this work provides a straightforward and feasible strategy for achieving efficient photothermal catalytic DRM and even other CH_(4)conversion implementations with long-term stability.展开更多
The hydrogenation of petroleum resin(PR)is an effective process to prepare high value-added hydrogenated PR(HPR).However,the preparation of non-noble metal-based catalysts with high catalytic activity for PR hydrogena...The hydrogenation of petroleum resin(PR)is an effective process to prepare high value-added hydrogenated PR(HPR).However,the preparation of non-noble metal-based catalysts with high catalytic activity for PR hydrogenation still remains a challenge.Herein,a La promoted Ni-based catalyst is reported through the thermal reduction of quaternary Ni La Mg Al-layered double hydroxides(Ni La Mg Al-LDHs).The incorporation of La is beneficial to the reduction and stability of Ni particles with reduced particle size,and the increased alkalinity effectively mitigates the breakage of molecular chains of PR.As a result,the La promoted Ni-based catalyst exhibits high catalytic activity and excellent stability for PR hydrogenation.A hydrogenation degree of 95.4%and 96.1%can be achieved for HC_(5)PR and HC_(9) PR with less reduced softening point,respectively.Notably,the hydrogenation degree still maintains at 92.7%even after 100 hours’reaction,much better than that without La incorporation or prepared using conventional impregnation method.展开更多
Highly active and selective Ni-based catalysts for partial oxidation of methane (POM) to syngas (CO/H,) have been studied and developed. Spectroscopic characterization by XRD, XPS, EPR, etc. demonstrated that under th...Highly active and selective Ni-based catalysts for partial oxidation of methane (POM) to syngas (CO/H,) have been studied and developed. Spectroscopic characterization by XRD, XPS, EPR, etc. demonstrated that under the POM reaction conditions, the Ni-components of the catalysts investigated were reduced and enriched on the surface to form metallic Ni0-phase. A comparative study of the first series of transition-metals showed that only Ni and Co have a high POM activity and selectivity, whereas the others (including Mn, Fe, Cu, etc. ) give mainly complete combustion products, Co, and H2O. The results favor the following viewpoints: the PoM activity is related with the rapidly changeable valence transitionmetal sites, M0/M2+ (e. g. Ni0/Ni2+ ), on the surface of the functioning catalysts;the transition-metal sites in zero-valence state seem to be responsible for the activation and dehydrogenation of methane by homolytic splitting of its C-H bonds on these sites. and the nature of rapidly changeable valence of the active sties is requisite for activation and rapid conversion of dioxygen.展开更多
A series of Ni/SBA-15 catalysts with Ni contents from 5 wt%–20 wt%and CaO-12.5%Ni/SBA-15 catalysts with CaO contents from 1.4 wt%– 9.8 wt%have been prepared.The structure of the catalysts was characterized using X-r...A series of Ni/SBA-15 catalysts with Ni contents from 5 wt%–20 wt%and CaO-12.5%Ni/SBA-15 catalysts with CaO contents from 1.4 wt%– 9.8 wt%have been prepared.The structure of the catalysts was characterized using X-ray diffraction（XRD）,N2 adsorption-desorption,transmission electron microscopy（TEM）and X-ray photoelectron spectroscopy（XPS）.The performance of catalytic steam reforming of the poplar leaves to the hydrogen-rich syngas was tested in a fixed-bed reactor.The results indicate that the 7.0wt%CaO-12.5wt%Ni/SBA-15 catalyst exhibits the best performance for the catalytic steam reforming of poplar leaves to hydrogen-rich syngas.The ratio of H2：CO can reach ca 5：1 in the hydrogen-rich syngas.The yield of H2 can reach 273.30 mL/g（poplar leaves）.In the CaO-Ni/SBA-15 catalyst,Ni active component mainly fills the role of catalytic steam reforming of the poplar leaves,and CaO active component mainly plays the role as water-gas shift and CO2 sorbent.展开更多
Kaolin as a raw material for mesoporous support was firstly modified by calcination,acid treatment,and then was used to prepare nickel catalysts.The amount of alumina which was activated in kaolin during thermal treat...Kaolin as a raw material for mesoporous support was firstly modified by calcination,acid treatment,and then was used to prepare nickel catalysts.The amount of alumina which was activated in kaolin during thermal treatment and then leached out in the acid was different.XRD pattern of the kaolin calcined at 600°C or 900°C exhibited only the diffraction peaks for amorphous silica and quartz while that calcined at 1100°C showed obvious peaks forγ-Al2 O3.Therefore,the nickel-based catalysts exhibited different physic-chemical properties.Atmospheric syngas methanation over the catalysts clarified an activity order of CA-1100 N CA-900 N CA-1400 N CA-600 N KA≈0 at temperatures of 350–650°C and a space velocity of 120 L·g-1·h-1.Metallic nickel with small diameter which has medium interaction with the modified kaolin and is well dispersed on the support would have reasonably good activity and carbon-resistance for syngas methanation.展开更多
Ligand modification of Ni-based catalysts by coordination of dicyandiamide to Ni metal leads to enhanced selectivity for the selective hydrogenation of halonitroaromatics.The selectivity of above 99.9%to aromatic halo...Ligand modification of Ni-based catalysts by coordination of dicyandiamide to Ni metal leads to enhanced selectivity for the selective hydrogenation of halonitroaromatics.The selectivity of above 99.9%to aromatic haloamines can be achieved at the conversion of 100%.The results of H_2-TPD and FT-IR experiments show that Ni^-H~＋ species possessing the properties of Lewis acid site on the surface of Raney Ni could be responsible for the hydrodehalogenation.When Raney Ni was treated by dicyandiamide,Ni^-H~＋ species interacted with N atom from the dicyandiamide.This interaction was stable even at reaction temperature,which reduced the possibility to form the intermediate state of Ar-Cl...H~＋Ni^-.And then C-Cl bond could not be polarized and activated.The hvdrodechlorination process was suppressed effectively.展开更多
Perovskites as host structures of cations were used in order to generate in situ active and stable catalysts for ethanol steam reforming. For this purpose,La_(1-x)Mg_xAl_(1-y)Ni_yO_3(x = 0.1; y = 0,0.1,0.2,0.3) perovs...Perovskites as host structures of cations were used in order to generate in situ active and stable catalysts for ethanol steam reforming. For this purpose,La_(1-x)Mg_xAl_(1-y)Ni_yO_3(x = 0.1; y = 0,0.1,0.2,0.3) perovskites were synthetized by the citrate method.Ni segregation is evident for a substitution level higher than 0. 2. The segregation of Ni as NiO generated species interacts with different metal-support after the reduction step. The y = 0.1 catalyst presents the highest H_2 yield value about 85% during reaction time,with low mean values of CH_4 and CO selectivities of 3.4% and 11%,respectively and a low carbon formation. The better performance of y = 0.1 catalyst could be attributed to the minor proportion of segregated phases,thus a controlled expulsion of Ni is successfully reached.展开更多
A series of Ni based catalysts with different supports and basic additives were prepared by sequential impregnation method. The catalysts were characterized by XRD, BET, H2-TPR and CO2-TPD techniques. It was found tha...A series of Ni based catalysts with different supports and basic additives were prepared by sequential impregnation method. The catalysts were characterized by XRD, BET, H2-TPR and CO2-TPD techniques. It was found that the introduction of basic additives enhanced the basicities of catalyats and promoted the dispersities of Ni particles by strong interaction between Ni2＋ and basic additives. Among the Ni based catalysts, 10%Ni/10%La203/ZrO2 showed the superior performance in sorbitol hydrogenolysis. The synergistic effect of Ni and La203 was proven to play an essential role in selective synthesis of EG and 1,2-PG. In the optimal reaction condition, the catalyst presented 100% sorbitol conversion and over 48% glycols （EG and 1,2-PG） yield. The kinetics study of polyols （sorbitol, xylitol and glycerol） hydrogenolysis showed that polyols with more hydroxyl number have higher activity and products distribution was final results of kinetic balance, which could give us some inspiration abeut how to change the products selectivity.展开更多
Co-precipitation method was selected for the preparation of Ni/Al_2O_3, Ni/ZrO_2 and Ni/CeO_2 catalysts, and their performances in methanation were investigated in this study. The structure and surface properties of t...Co-precipitation method was selected for the preparation of Ni/Al_2O_3, Ni/ZrO_2 and Ni/CeO_2 catalysts, and their performances in methanation were investigated in this study. The structure and surface properties of these catalysts were characterized by BET, XRD, H_2-TPD, TEM and H_2-TPR. The results showed that the catalytic activity at low temperature followed the order: Ni/Al_2O_3>Ni/ZrO_2>Ni/CeO_2. Ni/Al_2O_3 catalyst presented the best catalytic performance with the highest CH_4 selectivity of 94.5%. The characterization results indicated that the dispersion of the active component Ni was the main factor affecting the catalytic activity and the one with higher dispersion gave better performance.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
A method of synthesizing Ni-based catalysts supported on α-Al2O3-based foams was developed. The foams were impregnated with aqueous solutions of metal chlorides under an air atmosphere using an aerosol route. Separat...A method of synthesizing Ni-based catalysts supported on α-Al2O3-based foams was developed. The foams were impregnated with aqueous solutions of metal chlorides under an air atmosphere using an aerosol route. Separate procedures involved calcination to form oxides and drying to obtain chlorides on the foam surface. The synthesized samples were subsequently reduced with hydrogen. With respect to the Ni/Al2O3 catalysts, the chloride reduction route enabled the formation ofa Ni coating without agglomerates or cracks. Further research included catalyst modification by the addition of Pd, Cu, and Fe. The influences of the additives on the degree of reduction and on the low-temperature reduction effectiveness （533 and 633 K） were examined and compared for the catalysts obtained from oxides and chlorides. Greater degrees of reduction were achieved with chlorides, whereas Pd was the most effective modifier among those investigated. The reduction process was nearly complete at 533 K in the sample that contained 0.1wt% Pd. A lower reduction temperature was utilized, and the calcination step was avoided, which may enhance the economical and technological aspects of the developed catalyst production method.展开更多
RE-doped Ni-based catalysts were prepared by sol-gel method.These catalysts were applied to the reaction of CO2 reforming CH4 to syngas.The studies reveal that RE-doped ( RE = La, Ce, Sm, Yb) Ni-based catalysts show h...RE-doped Ni-based catalysts were prepared by sol-gel method.These catalysts were applied to the reaction of CO2 reforming CH4 to syngas.The studies reveal that RE-doped ( RE = La, Ce, Sm, Yb) Ni-based catalysts show higher catalytic activity than undoped Ni-based catalyst, and with the increasing of RE-doped quantity, the catalytic activity of catalysts exhibits regular changes.When RE-doped quantity is 0.2% ( molar ratio), the catalysts show the best catalytic activity.展开更多
Ni-based materials,widely recognized for their exceptional catalytic properties,experience structural transformations that profoundly influence their performance characteristics and operational stability.To deeply und...Ni-based materials,widely recognized for their exceptional catalytic properties,experience structural transformations that profoundly influence their performance characteristics and operational stability.To deeply understand the reconstruction mechanism of Ni-based catalysts,this review systematically summarizes the advanced strategies tailoring the dynamic reconstruction process,including electrochemical activation,defect engineering,partial etching,ionic doping,and heterostructure construction.Furthermore,we discuss the implications of these surface transformations on catalytic activity,highlighting their role in optimizing reaction pathways and enhancing overall efficiency in various electrooxidation reactions,such as oxygen evolution reaction(OER),urea oxidation reaction(UOR),glycerol oxidation reaction(GOR),hydroxymethylfurfural oxidation reaction(HMFOR),and ammonia oxidation reaction(AOR).By summarizing recent research findings,this review aims to provide a systematical summary of how surface dynamics can be harnessed to improve the design of Ni-based catalysts for a variety of electrooxidation applications,paving the way for advancements in energy conversion and storage technologies.展开更多
Nickel-based catalysts have emerged as crucial components in alkaline oxygen evolution reactions(OER)due to their exceptional catalytic performance and unique structural properties.However,the understanding of their c...Nickel-based catalysts have emerged as crucial components in alkaline oxygen evolution reactions(OER)due to their exceptional catalytic performance and unique structural properties.However,the understanding of their catalytic mechanisms remains incomplete.This review systematically explores the various types of Ni-based catalysts,including metal-organic frameworks(MOFs),perovskites,and layered double hydroxides(LDHs),while emphasizing their performance metrics.We critically assess the application of advanced in situ characterization techniques,such as in situ Raman spectroscopy and X-ray absorption spectroscopy(XAS),in elucidating the structural evolution and active species during the OER process.By addressing the interplay between catalyst structure and performance,this review aims to provide insights that drive future research efforts toward the optimization of Ni-based catalysts for sustainable hydrogen production.Key areas for potential research advancements are also identified.展开更多
Photothermal CO_(2) reduction is an efficient and sustainable catalytic path for CO_(2) treatment.Here,we successfully fabricated a novel series of Ni-based catalysts(Ni-x)via H2 reduction of NiAl-layered double hydro...Photothermal CO_(2) reduction is an efficient and sustainable catalytic path for CO_(2) treatment.Here,we successfully fabricated a novel series of Ni-based catalysts(Ni-x)via H2 reduction of NiAl-layered double hydroxide nanosheets at temperatures(x)ranging from 300 to 600°C.With the increase of the reduction temperature,the methane generation rate of the Ni-x catalyst for photothermal CO_(2) hydrogenation gradually increased under ultraviolet-visible-infrared(UV-vis-IR)irradiation in a flow-type system.The Ni-600 catalyst showed a CO_(2) conversion of 78.4%,offering a CH4 production rate of 278.8 mmol·g^(−1)h−1,with near 100%selectivity and 100 h long-term stability.Detailed characterization analyses showed metallic Ni nanoparticles supported on amorphous alumina are the catalytically active phase for CO_(2) methanation.This study provides a possibility for large-scale conversion and utilization of CO_(2) from a sustainable perspective.展开更多
A series of Ni/SBA-15 catalysts with Ni contents ranging from 5wt% to 20wt% as well as 10wt%Ni/10wt%CexZr1-xO2/SBA-15 （x=0, 0.5, 1） were prepared. The structures of the catalysts were characterized using XRD, TPR, T...A series of Ni/SBA-15 catalysts with Ni contents ranging from 5wt% to 20wt% as well as 10wt%Ni/10wt%CexZr1-xO2/SBA-15 （x=0, 0.5, 1） were prepared. The structures of the catalysts were characterized using XRD, TPR, TEM and BET techniques. The catalytic activities of the catalysts for steam reforming of methane were evaluated in a continuous flow microreactor. The results indicated that both the Ni/SBA-15 and the Ni/CexZr1-xO2/SBA-15 catalysts had good catalytic activities at at- mospheric pressure. The 10wt%Ni/SBA-15 catalyst exhibited excellent stability at 800 ℃ for time on stream of 740 h. After the reaction, carbon deposits were not formed on the surface of the catalyst. There existed a regular hexagonal mesoporous structure in the Ni/SBA-15 and the Ni/CexZr1-xO2/SBA-15 catalysts. The nickel species and the CexZr1-xO2 component were all confined in the SBA-15 mesopores. The CexZr1-xO2 could promote dispersion of the nickel species in the Ni/CexZr1-xO2/SBA-15 catalysts.展开更多
A series of Ni/SBA-15 catalysts with 5wt% to 15wt% Ni content as well as a series of 12.5%Ni/Cu/SBA-15 catalysts with 1% to 10% copper content were prepared by the impregnation method. The catalytic performance for pa...A series of Ni/SBA-15 catalysts with 5wt% to 15wt% Ni content as well as a series of 12.5%Ni/Cu/SBA-15 catalysts with 1% to 10% copper content were prepared by the impregnation method. The catalytic performance for partial oxidation of methane was investigated in a continuous flow microreactor under atmospheric pressure. The textural and chemical properties of the catalysts were characterized by XRD, TEM, BET and Hz-TPR techniques. The results indicated that the catalysts modified with Cu promoter showed better performance than those without modification. For the 12.5%Ni/2.5%/Cu/SBA-15 catalyst, at 850 ℃ the conversion of CH4 reached 97.9% and the selectivity of CO and H2 reached 98.0% and 96.0%, respectively. In XRD patterns of the Ni/Cu/SBA-15 catalyst with 7.5 to 10% Cu contents there were CuO characteristic peaks beside NiO characteristic peaks. The mesoporous structure of SBA-15 was retained in all of the catalysts. TPR analysis of the catalysts revealed that a strong interaction between Ni, Cu promoter and SBA-15 support may be existed. This interaction enhanced significantly the redox properties of the catalysts resulting in the higher catalytic activity.展开更多
文摘Recent research progress on the use of Ni-based catalysts supported by various carbon materials,such as carbon nanotubes,graphene,and activated carbon,for the hydrogenation of CO_(2)to CH4 is summarized.The influence of additives and surface modification methods on improving their catalytic performance is discussed as is the reaction mechanism,especially the structurefunction relationship produced by the carbon.The review provides a comprehensive directory for the rational design of carbon-supported Ni-based catalysts for the methanation of CO_(2).
基金supported by the Natural Science Foundation of Shanxi Province(202203021221155)the Foundation of National Key Laboratory of High Efficiency and Low Carbon Utilization of Coal(J23-24-902)。
文摘With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.
文摘Photothermal catalytic methane dry reforming(DRM)technology can convert greenhouse gases(i.e.CH_(4)and CO_(2))into syngas(i.e.H_(2)and CO),providing more opportunities for reducing the greenhouse effect and achieving carbon neutrality.In the DRM field,Ni-based catalysts attract wide attention due to their low cost and high activity.However,the carbon deposition over Ni-based catalysts always leads to rapid deactivation,which is still a main challenge.To improve the long-term stability of Ni-based catalysts,this work proposes a carbon-atom-diffusion strategy under photothermal conditions and investigates its effect on a Zn-doped Ni-based photothermal catalyst(Ni_(3)Zn@CeO_(2)).The photothermal catalytic behavior of Ni_(3)Zn@CeO_(2)can maintain more than 70 h in DRM reaction.And the photocatalytic DRM activity of Ni_(3)Zn@CeO_(2)is 1.2 times higher than thermal catalytic activity.Density functional theory(DFT)calculation and experimental characterizations indicate that Ni_(3)Zn promotes the diffusion of carbon atoms into the Ni_(3)Zn to form the Ni_(3)ZnC0.7 phase with body-centered cubic(bcc)structure,thus inhibiting carbon deposition.Further,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy and DFT calculation prove Ni_(3)Zn@CeO_(2)benefits the CH_(4)activation and inhibits the carbon deposition during the DRM process.Through inducing carbon atoms diffusion within the Ni_(3)Zn lattice,this work provides a straightforward and feasible strategy for achieving efficient photothermal catalytic DRM and even other CH_(4)conversion implementations with long-term stability.
基金financially supported by the National Natural Science Foundation of China(22078064)Natural Science Foundation of Fujian Province for Distinguished Young Scholar(2018J06002)。
文摘The hydrogenation of petroleum resin(PR)is an effective process to prepare high value-added hydrogenated PR(HPR).However,the preparation of non-noble metal-based catalysts with high catalytic activity for PR hydrogenation still remains a challenge.Herein,a La promoted Ni-based catalyst is reported through the thermal reduction of quaternary Ni La Mg Al-layered double hydroxides(Ni La Mg Al-LDHs).The incorporation of La is beneficial to the reduction and stability of Ni particles with reduced particle size,and the increased alkalinity effectively mitigates the breakage of molecular chains of PR.As a result,the La promoted Ni-based catalyst exhibits high catalytic activity and excellent stability for PR hydrogenation.A hydrogenation degree of 95.4%and 96.1%can be achieved for HC_(5)PR and HC_(9) PR with less reduced softening point,respectively.Notably,the hydrogenation degree still maintains at 92.7%even after 100 hours’reaction,much better than that without La incorporation or prepared using conventional impregnation method.
文摘Highly active and selective Ni-based catalysts for partial oxidation of methane (POM) to syngas (CO/H,) have been studied and developed. Spectroscopic characterization by XRD, XPS, EPR, etc. demonstrated that under the POM reaction conditions, the Ni-components of the catalysts investigated were reduced and enriched on the surface to form metallic Ni0-phase. A comparative study of the first series of transition-metals showed that only Ni and Co have a high POM activity and selectivity, whereas the others (including Mn, Fe, Cu, etc. ) give mainly complete combustion products, Co, and H2O. The results favor the following viewpoints: the PoM activity is related with the rapidly changeable valence transitionmetal sites, M0/M2+ (e. g. Ni0/Ni2+ ), on the surface of the functioning catalysts;the transition-metal sites in zero-valence state seem to be responsible for the activation and dehydrogenation of methane by homolytic splitting of its C-H bonds on these sites. and the nature of rapidly changeable valence of the active sties is requisite for activation and rapid conversion of dioxygen.
基金supported by the National Basic Research Program of China(No.2005CB221405)the National"863"Project of China(No.2006AA10Z425)
文摘A series of Ni/SBA-15 catalysts with Ni contents from 5 wt%–20 wt%and CaO-12.5%Ni/SBA-15 catalysts with CaO contents from 1.4 wt%– 9.8 wt%have been prepared.The structure of the catalysts was characterized using X-ray diffraction（XRD）,N2 adsorption-desorption,transmission electron microscopy（TEM）and X-ray photoelectron spectroscopy（XPS）.The performance of catalytic steam reforming of the poplar leaves to the hydrogen-rich syngas was tested in a fixed-bed reactor.The results indicate that the 7.0wt%CaO-12.5wt%Ni/SBA-15 catalyst exhibits the best performance for the catalytic steam reforming of poplar leaves to hydrogen-rich syngas.The ratio of H2：CO can reach ca 5：1 in the hydrogen-rich syngas.The yield of H2 can reach 273.30 mL/g（poplar leaves）.In the CaO-Ni/SBA-15 catalyst,Ni active component mainly fills the role of catalytic steam reforming of the poplar leaves,and CaO active component mainly plays the role as water-gas shift and CO2 sorbent.
基金Supported by the National Natural Science Foundation of China(21161140329)the National High Technology Research and Development Program of China(2015AA050502).
文摘Kaolin as a raw material for mesoporous support was firstly modified by calcination,acid treatment,and then was used to prepare nickel catalysts.The amount of alumina which was activated in kaolin during thermal treatment and then leached out in the acid was different.XRD pattern of the kaolin calcined at 600°C or 900°C exhibited only the diffraction peaks for amorphous silica and quartz while that calcined at 1100°C showed obvious peaks forγ-Al2 O3.Therefore,the nickel-based catalysts exhibited different physic-chemical properties.Atmospheric syngas methanation over the catalysts clarified an activity order of CA-1100 N CA-900 N CA-1400 N CA-600 N KA≈0 at temperatures of 350–650°C and a space velocity of 120 L·g-1·h-1.Metallic nickel with small diameter which has medium interaction with the modified kaolin and is well dispersed on the support would have reasonably good activity and carbon-resistance for syngas methanation.
基金the National Basic Research Program of China(973 Program)(No 2011CB710800)the National Natural Science Foundation of China(No20976164)
文摘Ligand modification of Ni-based catalysts by coordination of dicyandiamide to Ni metal leads to enhanced selectivity for the selective hydrogenation of halonitroaromatics.The selectivity of above 99.9%to aromatic haloamines can be achieved at the conversion of 100%.The results of H_2-TPD and FT-IR experiments show that Ni^-H~＋ species possessing the properties of Lewis acid site on the surface of Raney Ni could be responsible for the hydrodehalogenation.When Raney Ni was treated by dicyandiamide,Ni^-H~＋ species interacted with N atom from the dicyandiamide.This interaction was stable even at reaction temperature,which reduced the possibility to form the intermediate state of Ar-Cl...H~＋Ni^-.And then C-Cl bond could not be polarized and activated.The hvdrodechlorination process was suppressed effectively.
文摘Perovskites as host structures of cations were used in order to generate in situ active and stable catalysts for ethanol steam reforming. For this purpose,La_(1-x)Mg_xAl_(1-y)Ni_yO_3(x = 0.1; y = 0,0.1,0.2,0.3) perovskites were synthetized by the citrate method.Ni segregation is evident for a substitution level higher than 0. 2. The segregation of Ni as NiO generated species interacts with different metal-support after the reduction step. The y = 0.1 catalyst presents the highest H_2 yield value about 85% during reaction time,with low mean values of CH_4 and CO selectivities of 3.4% and 11%,respectively and a low carbon formation. The better performance of y = 0.1 catalyst could be attributed to the minor proportion of segregated phases,thus a controlled expulsion of Ni is successfully reached.
基金This work was supported by the National Natural Science Foundation of China （No.51376185 and No.51106108）, the National Basic Research Program of China （No.2012CB215304）, the National High Technology Research and Development Program of China （No.2012AA101806）, and the Natural Science Foundation of Guangdong Province （No.$2013010011612）.
文摘A series of Ni based catalysts with different supports and basic additives were prepared by sequential impregnation method. The catalysts were characterized by XRD, BET, H2-TPR and CO2-TPD techniques. It was found that the introduction of basic additives enhanced the basicities of catalyats and promoted the dispersities of Ni particles by strong interaction between Ni2＋ and basic additives. Among the Ni based catalysts, 10%Ni/10%La203/ZrO2 showed the superior performance in sorbitol hydrogenolysis. The synergistic effect of Ni and La203 was proven to play an essential role in selective synthesis of EG and 1,2-PG. In the optimal reaction condition, the catalyst presented 100% sorbitol conversion and over 48% glycols （EG and 1,2-PG） yield. The kinetics study of polyols （sorbitol, xylitol and glycerol） hydrogenolysis showed that polyols with more hydroxyl number have higher activity and products distribution was final results of kinetic balance, which could give us some inspiration abeut how to change the products selectivity.
基金financial support from the National Science and Technology Supporting Plan through contract (2015BAD15B06)the National Natural Science Foundation of China (51661145011)
文摘Co-precipitation method was selected for the preparation of Ni/Al_2O_3, Ni/ZrO_2 and Ni/CeO_2 catalysts, and their performances in methanation were investigated in this study. The structure and surface properties of these catalysts were characterized by BET, XRD, H_2-TPD, TEM and H_2-TPR. The results showed that the catalytic activity at low temperature followed the order: Ni/Al_2O_3>Ni/ZrO_2>Ni/CeO_2. Ni/Al_2O_3 catalyst presented the best catalytic performance with the highest CH_4 selectivity of 94.5%. The characterization results indicated that the dispersion of the active component Ni was the main factor affecting the catalytic activity and the one with higher dispersion gave better performance.
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.
基金financially supported by the Ministry of Education, Science and Technological Development of the Republic of Serbia and is a result of projects No. 34033 and No. 34023
文摘A method of synthesizing Ni-based catalysts supported on α-Al2O3-based foams was developed. The foams were impregnated with aqueous solutions of metal chlorides under an air atmosphere using an aerosol route. Separate procedures involved calcination to form oxides and drying to obtain chlorides on the foam surface. The synthesized samples were subsequently reduced with hydrogen. With respect to the Ni/Al2O3 catalysts, the chloride reduction route enabled the formation ofa Ni coating without agglomerates or cracks. Further research included catalyst modification by the addition of Pd, Cu, and Fe. The influences of the additives on the degree of reduction and on the low-temperature reduction effectiveness （533 and 633 K） were examined and compared for the catalysts obtained from oxides and chlorides. Greater degrees of reduction were achieved with chlorides, whereas Pd was the most effective modifier among those investigated. The reduction process was nearly complete at 533 K in the sample that contained 0.1wt% Pd. A lower reduction temperature was utilized, and the calcination step was avoided, which may enhance the economical and technological aspects of the developed catalyst production method.
文摘RE-doped Ni-based catalysts were prepared by sol-gel method.These catalysts were applied to the reaction of CO2 reforming CH4 to syngas.The studies reveal that RE-doped ( RE = La, Ce, Sm, Yb) Ni-based catalysts show higher catalytic activity than undoped Ni-based catalyst, and with the increasing of RE-doped quantity, the catalytic activity of catalysts exhibits regular changes.When RE-doped quantity is 0.2% ( molar ratio), the catalysts show the best catalytic activity.
基金supported by National Natural Science Foundation of China(Nos.52073199 and 52274304)。
文摘Ni-based materials,widely recognized for their exceptional catalytic properties,experience structural transformations that profoundly influence their performance characteristics and operational stability.To deeply understand the reconstruction mechanism of Ni-based catalysts,this review systematically summarizes the advanced strategies tailoring the dynamic reconstruction process,including electrochemical activation,defect engineering,partial etching,ionic doping,and heterostructure construction.Furthermore,we discuss the implications of these surface transformations on catalytic activity,highlighting their role in optimizing reaction pathways and enhancing overall efficiency in various electrooxidation reactions,such as oxygen evolution reaction(OER),urea oxidation reaction(UOR),glycerol oxidation reaction(GOR),hydroxymethylfurfural oxidation reaction(HMFOR),and ammonia oxidation reaction(AOR).By summarizing recent research findings,this review aims to provide a systematical summary of how surface dynamics can be harnessed to improve the design of Ni-based catalysts for a variety of electrooxidation applications,paving the way for advancements in energy conversion and storage technologies.
基金supported by the Fundamental Research Funds for the Central Universities(20822041H4082).
文摘Nickel-based catalysts have emerged as crucial components in alkaline oxygen evolution reactions(OER)due to their exceptional catalytic performance and unique structural properties.However,the understanding of their catalytic mechanisms remains incomplete.This review systematically explores the various types of Ni-based catalysts,including metal-organic frameworks(MOFs),perovskites,and layered double hydroxides(LDHs),while emphasizing their performance metrics.We critically assess the application of advanced in situ characterization techniques,such as in situ Raman spectroscopy and X-ray absorption spectroscopy(XAS),in elucidating the structural evolution and active species during the OER process.By addressing the interplay between catalyst structure and performance,this review aims to provide insights that drive future research efforts toward the optimization of Ni-based catalysts for sustainable hydrogen production.Key areas for potential research advancements are also identified.
基金The authors are grateful for financial support from the National Key Projects for Fundamental Research and Development of China(Nos.2018YFB1502002,2017YFA0206904,and 2017YFA0206900)the National Natural Science Foundation of China(Nos.51825205,51772305,21871279,21902168,and 52072382)+5 种基金the Beijing Natural Science Foundation(Nos.2191002,and 2194089)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB17000000)the Royal Society-Newton Advanced Fellowship(No.NA170422)the International Partnership Program of Chinese Academy of Sciences(Nos.GJHZ1819 and GJHZ201974)the K.C.Wong Education Foundation,the Central China Normal University(No.2020YBZZ019)the Youth Innovation Promotion Association of the CAS and the Open Fund of the Key Laboratory of Thermal Management and Energy Utilization of Aircraft,Ministry of Industry and Information Technology,Nanjing University of Aeronautics and Astronautics(No.CEPE2020014)。
文摘Photothermal CO_(2) reduction is an efficient and sustainable catalytic path for CO_(2) treatment.Here,we successfully fabricated a novel series of Ni-based catalysts(Ni-x)via H2 reduction of NiAl-layered double hydroxide nanosheets at temperatures(x)ranging from 300 to 600°C.With the increase of the reduction temperature,the methane generation rate of the Ni-x catalyst for photothermal CO_(2) hydrogenation gradually increased under ultraviolet-visible-infrared(UV-vis-IR)irradiation in a flow-type system.The Ni-600 catalyst showed a CO_(2) conversion of 78.4%,offering a CH4 production rate of 278.8 mmol·g^(−1)h−1,with near 100%selectivity and 100 h long-term stability.Detailed characterization analyses showed metallic Ni nanoparticles supported on amorphous alumina are the catalytically active phase for CO_(2) methanation.This study provides a possibility for large-scale conversion and utilization of CO_(2) from a sustainable perspective.
基金Financial funds from the Chinese Natural Science Foundation(Project No.20473009)the Beijing Natural Science Foundation(Project No.8062023)+1 种基金the National Basic Research Program of China(Project No.2005CB221405)the National"863"Project of China(No.2006 AA10Z425)are gratefully acknowledged.
文摘A series of Ni/SBA-15 catalysts with Ni contents ranging from 5wt% to 20wt% as well as 10wt%Ni/10wt%CexZr1-xO2/SBA-15 （x=0, 0.5, 1） were prepared. The structures of the catalysts were characterized using XRD, TPR, TEM and BET techniques. The catalytic activities of the catalysts for steam reforming of methane were evaluated in a continuous flow microreactor. The results indicated that both the Ni/SBA-15 and the Ni/CexZr1-xO2/SBA-15 catalysts had good catalytic activities at at- mospheric pressure. The 10wt%Ni/SBA-15 catalyst exhibited excellent stability at 800 ℃ for time on stream of 740 h. After the reaction, carbon deposits were not formed on the surface of the catalyst. There existed a regular hexagonal mesoporous structure in the Ni/SBA-15 and the Ni/CexZr1-xO2/SBA-15 catalysts. The nickel species and the CexZr1-xO2 component were all confined in the SBA-15 mesopores. The CexZr1-xO2 could promote dispersion of the nickel species in the Ni/CexZr1-xO2/SBA-15 catalysts.
基金supported by the National Basic Research Program of China (Project No. 2005CB221405)the National "863" Project of China (No.2006AA10Z425)
文摘A series of Ni/SBA-15 catalysts with 5wt% to 15wt% Ni content as well as a series of 12.5%Ni/Cu/SBA-15 catalysts with 1% to 10% copper content were prepared by the impregnation method. The catalytic performance for partial oxidation of methane was investigated in a continuous flow microreactor under atmospheric pressure. The textural and chemical properties of the catalysts were characterized by XRD, TEM, BET and Hz-TPR techniques. The results indicated that the catalysts modified with Cu promoter showed better performance than those without modification. For the 12.5%Ni/2.5%/Cu/SBA-15 catalyst, at 850 ℃ the conversion of CH4 reached 97.9% and the selectivity of CO and H2 reached 98.0% and 96.0%, respectively. In XRD patterns of the Ni/Cu/SBA-15 catalyst with 7.5 to 10% Cu contents there were CuO characteristic peaks beside NiO characteristic peaks. The mesoporous structure of SBA-15 was retained in all of the catalysts. TPR analysis of the catalysts revealed that a strong interaction between Ni, Cu promoter and SBA-15 support may be existed. This interaction enhanced significantly the redox properties of the catalysts resulting in the higher catalytic activity.
