Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3...Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.展开更多
Carbon-supported mercury catalysts are extensivelyemployed in calcium carbide-based polyvinyl chloride(PVC)industries,but the usage of mercury-based catalysts can pose an environmental threat due to the release of mer...Carbon-supported mercury catalysts are extensivelyemployed in calcium carbide-based polyvinyl chloride(PVC)industries,but the usage of mercury-based catalysts can pose an environmental threat due to the release of mercury into the surrounding area during the operation period.In this study,a highly active and stable mercury-based catalyst was developed,utilizing the nitrogen atom of the support as the anchor site to enhance the interaction between active sites(HgCl_(2))and the carbon support(N-AC).Thermal loss rate testing and thermogravimetric analysis results demonstrate that,compared to commercial activated carbon,N-doped carbon can effectively increase the heat stability of HgCl_(2).The obtained mercury-based catalysts(HgCl_(2)/N-AC)exhibit significant catalytic performance,achieving 2.5 times the C2H2 conversion of conventional HgCl_(2)/AC catalysts.Experimental analysis combined with theoretical calculations reveals that,contrary to the Eley-Rideal(ER)mechanism of HgCl_(2)/AC,the HgCl_(2)/N-AC catalyst follows the Langmuir-Hinshelwood(LH)adsorption mechanism.The nitrogen sites and HgCl_(2) on the catalyst enhance the adsorption capabilities of the HCl and C2H2,thereby improving the catalytic performance.Based on the modification of the active center by these solid ligands,the loading amount of HgCl_(2) on the catalyst can be further reduced from the current 6.5%to 3%.Considering the absence of successful industrial applications for mercury-free catalysts,and based on the current annual consumption of commercial mercury chloride catalysts in the PVC industry,the widespread adoption of this technology could annually reduce the usage of chlorine mercury by 500 tons,making a notable contribution to mercury compliance,reduction,and emissions control in China.It also serves as a bridge between mercury-free and low-mercury catalysts.Moreover,this solid ligand technology can assist in the application research of mercury-free catalysts.展开更多
The electrochemical carbon dioxide reduction reaction(CO_(2)RR)can convert carbon dioxide into highvalue chemical substances and fuels by utilizing renewable electricity,which can not only complete the carbon cycle bu...The electrochemical carbon dioxide reduction reaction(CO_(2)RR)can convert carbon dioxide into highvalue chemical substances and fuels by utilizing renewable electricity,which can not only complete the carbon cycle but also effectively alleviate the problems of global warming and energy shortage.Nickelbased catalysts hold great promise and unbeatable merits for the electroreduction of carbon dioxide due to their excellent catalytic properties and activity.However,there were few review papers on the application of nickel-based catalysts in carbon dioxide electroreduction.This paper,therefore,presents the current status of research on nickel-based catalysts in carbon dioxide electroreduction categorized by different products.First,the advantages of CO_(2) electroreduction and nickel-based catalysts as well as the basic principles of CO_(2) electroreduction are presented;then the different types of nickel-based catalysts that can convert CO_(2) into different products are described in detail,including their syntheses,performances,and mechanisms.Finally,the common features of nickel-based catalysts towards different carbon dioxide electroreduction products,as well as the outlooks for the development of nickel-based catalysts will be summarized.It is highly expected that this review will help in the future research and development of nickel-based catalysts towards CO_(2) conversion.展开更多
Exploring efficient transition-metal-based electrocatalysts is critical for the wide application of electrochemical hydrogen generation technology.Although the phase displays prominent influence on their performance,i...Exploring efficient transition-metal-based electrocatalysts is critical for the wide application of electrochemical hydrogen generation technology.Although the phase displays prominent influence on their performance,it remains a major challenge to achieve phase regulation in the same synthesis method and elucidate the intrinsic relationship between the phase and activity.Herein,we developed a sulfur induced electrodeposition strategy to achieve the precise phase regulation of nickel-based materials from Ni(OH)_(2)to Ni and Ni_(3)S_(2).S atoms can be introduced into Ni and Ni(OH)_(2)due to sulfur inducement,and the S proportion is finely controlled via changing the deposition parameters.Importantly,the obtained S-Ni catalyst displays enhanced hydrogen evolution activity with an ultralow overpotential of 27 mV at 10 mA cm^(-2),which is superior to the S-Ni(OH)_(2),Ni_(3)S_(2),and even Pt/C.Density functional theory(DFT)calculations disclose the S-Ni catalyst exhibits optimal charge state and local coordination,remarkably optimizing the water adsorption and Ni-H^(*)binding energy.This work provides new insights into phase regulation in electrodeposition and an understanding of the intrinsic relationship between phase and activity.展开更多
Herein,three supported catalysts,CuO/Al_(2)O_(3),CeO_(2)/Al_(2)O_(3),and CuO-CeO_(2)/Al_(2)O_(3),were synthesized by the convenient impregnation method to reveal the effect of CeO_(2)addition on catalytic performance ...Herein,three supported catalysts,CuO/Al_(2)O_(3),CeO_(2)/Al_(2)O_(3),and CuO-CeO_(2)/Al_(2)O_(3),were synthesized by the convenient impregnation method to reveal the effect of CeO_(2)addition on catalytic performance and reaction mechanism for toluene oxidation.Compared with CuO/Al_(2)O_(3),the T_(50)and T_(90)(the temperatures at 50%and 90%toluene conversion,respectively)of CuO-CeO_(2)/Al_(2)O_(3)were reduced by 33 and 39°C,respectively.N_(2)adsorptiondesorption experiment,XRD,SEM,EDS mapping,Raman,EPR,H_(2)-TPR,O_(2)-TPD,XPS,NH_(3)-TPD,Toluene-TPD,and in-situ DRIFTS were conducted to characterize these catalysts.The excellent catalytic performance of CuO-CeO_(2)/Al_(2)O_(3)could be attributed to its strong coppercerium interaction and high oxygen vacancies concentration.Moreover,in-situ DRIFTS proved that CuO-CeO_(2)/Al_(2)O_(3)promoted the conversion of toluene to benzoate and accelerated the deep degradation path of toluene.This work provided valuable insights into the development of efficient and economical catalysts for volatile organic compounds.展开更多
Volatile organic compounds(VOCs)exhausted from industrial processes are the major atmospheric pollutants,which could destroy the ecological environment and make hazards to human health seriously.Catalytic oxidation is...Volatile organic compounds(VOCs)exhausted from industrial processes are the major atmospheric pollutants,which could destroy the ecological environment and make hazards to human health seriously.Catalytic oxidation is regarded as the most competitive strategy for the efficient elimination of low-concentration VOCs.Supported noble metal catalysts are preferred catalysts due to their excellent low-temperature catalytic activity.To further lower the cost of catalysts,single atom catalysts(SAC)have been fabricated and extensively studied for application in VOCs oxidation due to their 100%atom-utilization efficiency and unique catalytic performance.In this review,we comprehensively summarize the recent advances in supported noble metal(e.g.,Pt,Pd,Au,and Ag)catalysts and SAC for VOCs oxidation since 2015.Firstly,this paper focuses on some important influencing factors that affect the activity of supported noble metal catalysts,including particle size,valence state and dispersion of noble metals,properties of the support,metal oxide/ion modification,preparation method,and pretreatment conditions of catalysts.Secondly,we briefly summarize the catalytic performance of SAC for typical VOCs.Finally,we conclude the key influencing factors and provide the prospects and challenges of VOCs oxidation.展开更多
Single-walled carbon nanotubes(SWNTs)with enriched(n,m)species are in high demand for various advanced applications.Since the SWNT structure is largely influenced by the chemistry of the active catalyst during growth ...Single-walled carbon nanotubes(SWNTs)with enriched(n,m)species are in high demand for various advanced applications.Since the SWNT structure is largely influenced by the chemistry of the active catalyst during growth process,exploiting novel catalyst with bias towards specific SWNT chiralities has been challenging.In this work,we introduce a vanadium catalyst supported by mesoporous magnesia(V-MgO)for the selective growth of SWNTs using CO chemical vapor deposition(CVD).At a reaction temperature of 650℃,the(6,5)SWNT content reaches an impressive 67.9%among all semiconducting species,exceeding the selectivity of many commercial SWNT products.Post-CVD analysis reveals that the catalyst transforms into vanadium carbide(VC),which acts as a nucleation site for SWNT growth.Molecular dynamics simulations indicate that the energy at the SWNT-VC interface and the growth kinetics of SWNTs contribute to the chirality selectivity.This research opens up possibilities for the selective synthesis of SWNTs using cost-effective early transition metals,illuminating their future applications in fields such as bioimaging.展开更多
The reductive transformation of furfural （FAL） into furfuryl alcohol （FOL） is an attractive route for the use of renewable bio‐sources but it suffers from the heavy use of H2. We describe here a highly efficient ...The reductive transformation of furfural （FAL） into furfuryl alcohol （FOL） is an attractive route for the use of renewable bio‐sources but it suffers from the heavy use of H2. We describe here a highly efficient reduction protocol for converting aqueous FAL to FOL. A single phase rutile TiO2 support with a gold catalyst （Au/TiO2‐R） that used CO/H2O as the hydrogen source catalyze this reduction efficiently under mild conditions. By eliminating the consumption of fossil fuel‐derived H2, our pro‐cess has the benefit afforded by using CO as a convenient and cost competitive reducing reagent.展开更多
A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potenti...A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt （Ⅳ） and Fe （Ⅱ） precursors as driving force. The formed Fe3O4 nanoparticles （NPs） effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe304 nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe3O4 catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of einnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120 ℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.展开更多
A series of Pd catalysts were prepared on different supports（Fe2O3,SiO2,ZnO,MgO,Al2O3,carbon,and Amberlyst-45） and used in the selective hydrogenation of phenol to cyclohexanone in water.The Amberlyst-45 supported P...A series of Pd catalysts were prepared on different supports（Fe2O3,SiO2,ZnO,MgO,Al2O3,carbon,and Amberlyst-45） and used in the selective hydrogenation of phenol to cyclohexanone in water.The Amberlyst-45 supported Pd catalyst（Pd/A-45） was highly active and selective under mild conditions（40-100 ℃,0.2-1 MPa）,giving a selectivity of cyclohexanone higher than 89%even at complete conversion of phenol.Experiments with different Pd loadings（or different particle sizes） confirmed that the formation of cyclohexanone was a structure sensitive reaction,and Pd particles of12-14 nm on Amberlyst-45 gave better selectivity and stability.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
A carbon nanotube-supported NiP amorphous catalyst （NiP/CNT） was prepared by induced reduction. Benzene hydrogenation was used as a probe reaction for the study of catalytic activity. The effects of the support on t...A carbon nanotube-supported NiP amorphous catalyst （NiP/CNT） was prepared by induced reduction. Benzene hydrogenation was used as a probe reaction for the study of catalytic activity. The effects of the support on the activity and thermal stability of the supported catalyst were discussed based on various characterizations, including XRD, TEM, ICP, XPS, H2-TPD, and DTA. In comparison with the NiP amorphous alloy, the benzene conversion on NiP/CNT catalyst was lower, but the specific activity of NiP/CNT was higher, which is attributed to the dispersion produced by the support, an electron-donating effect, and the hydrogen-storage ability of CNT. The NiP/CNT thermal stability was improved because of the dispersion and electronic effects and the good heat-conduction ability of the CNT support.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
A series of carbon nanotubes-supported K-Co-Mo catalysts were prepared by a sol-gel method combined with incipient wetness impregnation. The catalyst structures were characterized by X-ray diffraction, N2 adsorption-d...A series of carbon nanotubes-supported K-Co-Mo catalysts were prepared by a sol-gel method combined with incipient wetness impregnation. The catalyst structures were characterized by X-ray diffraction, N2 adsorption-desorption, transmission electron microscopy and H2-TPD, and its catalytic performance toward the synthesis of higher alcohols from syngas was investigated. The as-prepared catalyst particles had a low crystallization degree and high dispersion on the outer and inner surface of CNTs. The uniform mesoporous structure of CNTs increased the diffusion rate of reactants and products, thus promoting the reaction conversion. Furthermore, the incorporation of CNTs support led to a high capability of hydrogen absorption and spillover and promoted the formation of alkyl group, which served as the key intermediate for the alcohol formation and carbon chain growth. Benefiting from these characteristics, the CNTs supported Mo-based catalyst showed the excellent catalytic performance for the higher alcohols synthesis as compared to the unsupported catalyst and activated carbon supported catalyst.展开更多
A series of perovskite type oxides and supported Ag catalysts were prepared, and characterized by X ray diffraction (XRD) and X ray photoelectron spectroscopy (XPS). The catalytic activities of the catalyst...A series of perovskite type oxides and supported Ag catalysts were prepared, and characterized by X ray diffraction (XRD) and X ray photoelectron spectroscopy (XPS). The catalytic activities of the catalysts as well as influencing factors on catalytic activity have been investigated for the simultaneous removal of NOx and diesel soot particulate. An increase in catalytic activity for the selective reduction of NOx was observed with Ag addition in these perovskite oxides, especially with 5% Ag loading. This catalyst could be a promising candidate of catalytic material for the simultaneous elimination of NOx and diesel soot.展开更多
Au]Cel_xZrxO2 catalysts （x = 0-0.8） were prepared by a deposition-precipitation method using Cel_xZrxO2 nanoparticles as supports with variable Ce and Zr contents. Their structures were characterized by complimentar...Au]Cel_xZrxO2 catalysts （x = 0-0.8） were prepared by a deposition-precipitation method using Cel_xZrxO2 nanoparticles as supports with variable Ce and Zr contents. Their structures were characterized by complimentary means such as X-ray diffraction, Raman, scanning trans- mission electron microscopy and X-ray photoelectron spectroscopy （XPS）. These Au catalysts possessed similar sizes and crystalline phases of Cel_xZrzO2 supports as well as similar sizes and oxidation states of Au nanoparticles. The oxidation state of Au nanoparticles was dominated by Au~ especially in CO oxidation. Their activities were examined in CO oxidation at different temperatures in the range of 303-333 K. The CO oxidation rates normalized per Au atoms increased with the increasing Ce contents, and reached the maximum value over Au/CeO2. Such change was in parallel with the change in the oxygen storage capacity values, i.e. the amounts of active oxygen species on Au/Cel_zZrzO2 catalysts. The excellent correlation between the two properties of the catalysts suggests that the intrinsic support effects on the CO oxidation rates is related to the effects on the adsorption and activation of O2 on Au/Cel_xZrxO2 catalysts. Such understanding on the support effects may be useful for designing more active Au catalysts, for example, by tuning the redox properties of oxide supports.展开更多
Ni catalysts supported on various mixed oxides of Al2O3 with rare earth oxide and transitional metal oxides were synthesized. The studies focused on the measurement of the autothermal reforming of methane to hydrogen ...Ni catalysts supported on various mixed oxides of Al2O3 with rare earth oxide and transitional metal oxides were synthesized. The studies focused on the measurement of the autothermal reforming of methane to hydrogen over Ni catalysts supported on the mixed oxide ZrxCe30-xAl70Oδ （x-=5, 10, 15）. The catalytic performance of Ni/Zr10Ce20Al70Oδ was better than that of other catalysts. XRD results showed that the addition of Zr to Ni/Ce30Al70Oδ prevented the formation of NiAl2O4 and facilitated the dispersion of NiO. Effects of CuO addition to Zr10Ce20Al70Oδ were also investigated. The activity of Ni catalyst supported on CuO-ZrO2-CeO2-Al2O3 was somewhat affected and the Ni/Cu5Zr10Ce20Al65Oδ showed the best catalytic performance with the highest CH4 conversion, yield of H2, selectivity for H2 and H2/CO production ratio in operation temperatures ranging from 650 to 750 ℃.展开更多
The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffrac...The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR）, temperature-programmed desorption of hydrogen （H2-TPD） and activity evaluation, the physico-chemical and catalytic properties of the catalysts were investigated. Among the catalysts tested, the SiO2 supported nickel catalyst showed the highest activity and selectivity towards m-phenylenediamine, over which 97.3% m-dinitrobenzene conversion and 95.1% m-phenylenediamine yield were obtained at 373K under hydrogen pressure of 2.6MPa after reaction for 6 h when using ethanol as solvent. Although TiO2 and diatomite supported nickel catalysts also presented high activity, they had lower selectivity towards m-phenylenediamine. As for γ-Al2O3 and MgO supported catalysts were almost inactive for the object reaction. It was shown that both the activity and selectivity of the catalysts were strongly depended on the interaction between nickel and the support. The higher activities of Ni/SiO2, Ni/TiO2 and Ni/diatomite could be attributed to the weaker metal-support interaction, on which Ni species presented as crystallized Ni metal particles. On the other hand, there existed strong metal-support interaction in Ni/MgO and Ni γ-Al2O3, which causes these catalysts more difficult to be reduced and the availability of Ni active sites decreased, resulting in their low catalytic activity.展开更多
Most of volatile organic compounds(VOCs)are harmful to the atmosphere and human health.Cata‐lytic combustion is an effective way to eliminate VOCs.The key issue is the availability of high per‐formance catalysts.Man...Most of volatile organic compounds(VOCs)are harmful to the atmosphere and human health.Cata‐lytic combustion is an effective way to eliminate VOCs.The key issue is the availability of high per‐formance catalysts.Many catalysts including transition metal oxides,mixed metal oxides,and sup‐ported noble metals have been developed.Among these catalysts,the porous ones attract much attention.In this review,we focus on recent advances in the synthesis of ordered mesoporous and macroporous transition metal oxides,perovskites,and supported noble metal catalysts and their catalytic oxidation of VOCs.The porous catalysts outperformed their bulk counterparts.This excel‐lent catalytic performance was due to their high surface areas,high concentration of adsorbed oxy‐gen species,low temperature reducibility,strong interaction between noble metal and support and highly dispersed noble metal nanoparticles and unique porous structures.Catalytic oxidation of carbon monoxide over typical catalysts was also discussed.We made conclusive remarks and pro‐posed future work for the removal of VOCs.展开更多
Propylene slurry polymerization with a MgCl2-supported Ziegler-Natta catalyst containing internal electron donor was conducted after different durations of pre-contact of the catalyst with triethylaluminum cocatalyst....Propylene slurry polymerization with a MgCl2-supported Ziegler-Natta catalyst containing internal electron donor was conducted after different durations of pre-contact of the catalyst with triethylaluminum cocatalyst. The number of active centers([C*]/[Ti])was determined by quenching the polymerization with 2-thiophenecarbonyl chloride and measuring sulfur content in the polymer. The pre-contact treatment caused selective deactivation of a part of active centers with low stereoselectivity and much lower activity in the initial stage of polymerization as compared with the polymerization run without the pre-contact stage. The active center concentration and polymerization activity decreased with prolonging of the pre-contact stage. The proportion of stereoselective active centers was increased by prolonging the pre-contact stage, so the isotacticity of produced polypropylene was enhanced. Release of active centers through catalyst particle fragmentation was significantly retarded, and the polymerization rate curve changed from decay type to induction type by the precontact treatment. In the induction period both non-stereoselective and stereoselective active centers were released and activated, resulting in gradual reduction of the polymer’s isotacticity in the first 5-10 min of polymerization. Selective deactivation of non-stereoselective active centers also took place in propylene polymerization using the catalyst without pre-contacting with the cocatalyst. In this case, the polymerization rate decayed with time after a short induction period of 2-5 min. Over reduction of the active center precursors with low stereoselectivity by triethylaluminum was considered as the reason for their deactivation during the pre-contact or the polymerization processes.展开更多
基金Research Institute for Smart Energy(CDB2)the grant from the Research Institute for Advanced Manufacturing(CD8Z)+4 种基金the grant from the Carbon Neutrality Funding Scheme(WZ2R)at The Hong Kong Polytechnic Universitysupport from the Hong Kong Polytechnic University(CD9B,CDBZ and WZ4Q)the National Natural Science Foundation of China(22205187)Shenzhen Municipal Science and Technology Innovation Commission(JCYJ20230807140402006)Start-up Foundation for Introducing Talent of NUIST and Natural Science Foundation of Jiangsu Province of China(BK20230426).
文摘Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.
基金supported by the National Key Research and Development Program of China(2024YFC3907904).
文摘Carbon-supported mercury catalysts are extensivelyemployed in calcium carbide-based polyvinyl chloride(PVC)industries,but the usage of mercury-based catalysts can pose an environmental threat due to the release of mercury into the surrounding area during the operation period.In this study,a highly active and stable mercury-based catalyst was developed,utilizing the nitrogen atom of the support as the anchor site to enhance the interaction between active sites(HgCl_(2))and the carbon support(N-AC).Thermal loss rate testing and thermogravimetric analysis results demonstrate that,compared to commercial activated carbon,N-doped carbon can effectively increase the heat stability of HgCl_(2).The obtained mercury-based catalysts(HgCl_(2)/N-AC)exhibit significant catalytic performance,achieving 2.5 times the C2H2 conversion of conventional HgCl_(2)/AC catalysts.Experimental analysis combined with theoretical calculations reveals that,contrary to the Eley-Rideal(ER)mechanism of HgCl_(2)/AC,the HgCl_(2)/N-AC catalyst follows the Langmuir-Hinshelwood(LH)adsorption mechanism.The nitrogen sites and HgCl_(2) on the catalyst enhance the adsorption capabilities of the HCl and C2H2,thereby improving the catalytic performance.Based on the modification of the active center by these solid ligands,the loading amount of HgCl_(2) on the catalyst can be further reduced from the current 6.5%to 3%.Considering the absence of successful industrial applications for mercury-free catalysts,and based on the current annual consumption of commercial mercury chloride catalysts in the PVC industry,the widespread adoption of this technology could annually reduce the usage of chlorine mercury by 500 tons,making a notable contribution to mercury compliance,reduction,and emissions control in China.It also serves as a bridge between mercury-free and low-mercury catalysts.Moreover,this solid ligand technology can assist in the application research of mercury-free catalysts.
文摘The electrochemical carbon dioxide reduction reaction(CO_(2)RR)can convert carbon dioxide into highvalue chemical substances and fuels by utilizing renewable electricity,which can not only complete the carbon cycle but also effectively alleviate the problems of global warming and energy shortage.Nickelbased catalysts hold great promise and unbeatable merits for the electroreduction of carbon dioxide due to their excellent catalytic properties and activity.However,there were few review papers on the application of nickel-based catalysts in carbon dioxide electroreduction.This paper,therefore,presents the current status of research on nickel-based catalysts in carbon dioxide electroreduction categorized by different products.First,the advantages of CO_(2) electroreduction and nickel-based catalysts as well as the basic principles of CO_(2) electroreduction are presented;then the different types of nickel-based catalysts that can convert CO_(2) into different products are described in detail,including their syntheses,performances,and mechanisms.Finally,the common features of nickel-based catalysts towards different carbon dioxide electroreduction products,as well as the outlooks for the development of nickel-based catalysts will be summarized.It is highly expected that this review will help in the future research and development of nickel-based catalysts towards CO_(2) conversion.
基金supported by the National Natural Science Foundation of China(52271210,22179032,52171176)。
文摘Exploring efficient transition-metal-based electrocatalysts is critical for the wide application of electrochemical hydrogen generation technology.Although the phase displays prominent influence on their performance,it remains a major challenge to achieve phase regulation in the same synthesis method and elucidate the intrinsic relationship between the phase and activity.Herein,we developed a sulfur induced electrodeposition strategy to achieve the precise phase regulation of nickel-based materials from Ni(OH)_(2)to Ni and Ni_(3)S_(2).S atoms can be introduced into Ni and Ni(OH)_(2)due to sulfur inducement,and the S proportion is finely controlled via changing the deposition parameters.Importantly,the obtained S-Ni catalyst displays enhanced hydrogen evolution activity with an ultralow overpotential of 27 mV at 10 mA cm^(-2),which is superior to the S-Ni(OH)_(2),Ni_(3)S_(2),and even Pt/C.Density functional theory(DFT)calculations disclose the S-Ni catalyst exhibits optimal charge state and local coordination,remarkably optimizing the water adsorption and Ni-H^(*)binding energy.This work provides new insights into phase regulation in electrodeposition and an understanding of the intrinsic relationship between phase and activity.
基金supported by the Science and Technology Program of Guangzhou,China(No.202002020020)the National Natural Science Foundation of China(Nos.51878292 and 42002035).
文摘Herein,three supported catalysts,CuO/Al_(2)O_(3),CeO_(2)/Al_(2)O_(3),and CuO-CeO_(2)/Al_(2)O_(3),were synthesized by the convenient impregnation method to reveal the effect of CeO_(2)addition on catalytic performance and reaction mechanism for toluene oxidation.Compared with CuO/Al_(2)O_(3),the T_(50)and T_(90)(the temperatures at 50%and 90%toluene conversion,respectively)of CuO-CeO_(2)/Al_(2)O_(3)were reduced by 33 and 39°C,respectively.N_(2)adsorptiondesorption experiment,XRD,SEM,EDS mapping,Raman,EPR,H_(2)-TPR,O_(2)-TPD,XPS,NH_(3)-TPD,Toluene-TPD,and in-situ DRIFTS were conducted to characterize these catalysts.The excellent catalytic performance of CuO-CeO_(2)/Al_(2)O_(3)could be attributed to its strong coppercerium interaction and high oxygen vacancies concentration.Moreover,in-situ DRIFTS proved that CuO-CeO_(2)/Al_(2)O_(3)promoted the conversion of toluene to benzoate and accelerated the deep degradation path of toluene.This work provided valuable insights into the development of efficient and economical catalysts for volatile organic compounds.
基金supported by Beijing Natural Science Foundation(No.8244060)China Postdoctoral Science Foundation(No.2023M730143)+3 种基金the National Natural Science Foundation of China(No.22425601)the National Key R&D Program of China(No.2023YFB3810801)Beijing Nova Program(No.20240484659)the R&D Program of Beijing Municipal Education Commission(No.KZ202210005011).
文摘Volatile organic compounds(VOCs)exhausted from industrial processes are the major atmospheric pollutants,which could destroy the ecological environment and make hazards to human health seriously.Catalytic oxidation is regarded as the most competitive strategy for the efficient elimination of low-concentration VOCs.Supported noble metal catalysts are preferred catalysts due to their excellent low-temperature catalytic activity.To further lower the cost of catalysts,single atom catalysts(SAC)have been fabricated and extensively studied for application in VOCs oxidation due to their 100%atom-utilization efficiency and unique catalytic performance.In this review,we comprehensively summarize the recent advances in supported noble metal(e.g.,Pt,Pd,Au,and Ag)catalysts and SAC for VOCs oxidation since 2015.Firstly,this paper focuses on some important influencing factors that affect the activity of supported noble metal catalysts,including particle size,valence state and dispersion of noble metals,properties of the support,metal oxide/ion modification,preparation method,and pretreatment conditions of catalysts.Secondly,we briefly summarize the catalytic performance of SAC for typical VOCs.Finally,we conclude the key influencing factors and provide the prospects and challenges of VOCs oxidation.
基金financially supported by the Key Basic Research Project of Shandong Province(No.ZR2019ZD49)Taishan Scholar Foundation of Shandong Province(No.tstp20230627)Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences。
文摘Single-walled carbon nanotubes(SWNTs)with enriched(n,m)species are in high demand for various advanced applications.Since the SWNT structure is largely influenced by the chemistry of the active catalyst during growth process,exploiting novel catalyst with bias towards specific SWNT chiralities has been challenging.In this work,we introduce a vanadium catalyst supported by mesoporous magnesia(V-MgO)for the selective growth of SWNTs using CO chemical vapor deposition(CVD).At a reaction temperature of 650℃,the(6,5)SWNT content reaches an impressive 67.9%among all semiconducting species,exceeding the selectivity of many commercial SWNT products.Post-CVD analysis reveals that the catalyst transforms into vanadium carbide(VC),which acts as a nucleation site for SWNT growth.Molecular dynamics simulations indicate that the energy at the SWNT-VC interface and the growth kinetics of SWNTs contribute to the chirality selectivity.This research opens up possibilities for the selective synthesis of SWNTs using cost-effective early transition metals,illuminating their future applications in fields such as bioimaging.
基金supported by the National Natural Science Foundation of China (21273044, 21473035, 91545108)the Research Fund for the Doctoral Program of Higher Education (2012007000011)+2 种基金SINOPEC (X514005)Science & Technology Commission of Shanghai Municipality (08DZ2270500)the Open Project of State Key Laboratory of Chemical Engineering (SKL-ChE-15C02)~~
文摘The reductive transformation of furfural （FAL） into furfuryl alcohol （FOL） is an attractive route for the use of renewable bio‐sources but it suffers from the heavy use of H2. We describe here a highly efficient reduction protocol for converting aqueous FAL to FOL. A single phase rutile TiO2 support with a gold catalyst （Au/TiO2‐R） that used CO/H2O as the hydrogen source catalyze this reduction efficiently under mild conditions. By eliminating the consumption of fossil fuel‐derived H2, our pro‐cess has the benefit afforded by using CO as a convenient and cost competitive reducing reagent.
基金This work is supported by the National Natural Science Foundation of China （No.51372248, No.51432009 and No.51502297）, Instrument Developing Project of the Chinese Academy of Sciences （No.yz201421）, the CAS/SAFEA International Partnership Program for Creative Research Teams of Chinese Academy of Sciences, China.
文摘A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt （Ⅳ） and Fe （Ⅱ） precursors as driving force. The formed Fe3O4 nanoparticles （NPs） effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe304 nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe3O4 catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of einnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120 ℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.
基金supported by the National Natural Science Foundation of China(21473155,21273198,21073159)the Natural Science Foundation of Zhejiang Province(LZ12B03001)~~
文摘A series of Pd catalysts were prepared on different supports（Fe2O3,SiO2,ZnO,MgO,Al2O3,carbon,and Amberlyst-45） and used in the selective hydrogenation of phenol to cyclohexanone in water.The Amberlyst-45 supported Pd catalyst（Pd/A-45） was highly active and selective under mild conditions（40-100 ℃,0.2-1 MPa）,giving a selectivity of cyclohexanone higher than 89%even at complete conversion of phenol.Experiments with different Pd loadings（or different particle sizes） confirmed that the formation of cyclohexanone was a structure sensitive reaction,and Pd particles of12-14 nm on Amberlyst-45 gave better selectivity and stability.
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.
基金Supported by the National Natural Science Foundation of China (No. 20263003)Natural Science Foundation of Jiangxi province (No. 0250009)
文摘A carbon nanotube-supported NiP amorphous catalyst （NiP/CNT） was prepared by induced reduction. Benzene hydrogenation was used as a probe reaction for the study of catalytic activity. The effects of the support on the activity and thermal stability of the supported catalyst were discussed based on various characterizations, including XRD, TEM, ICP, XPS, H2-TPD, and DTA. In comparison with the NiP amorphous alloy, the benzene conversion on NiP/CNT catalyst was lower, but the specific activity of NiP/CNT was higher, which is attributed to the dispersion produced by the support, an electron-donating effect, and the hydrogen-storage ability of CNT. The NiP/CNT thermal stability was improved because of the dispersion and electronic effects and the good heat-conduction ability of the CNT support.
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This work was supported by National Natural Science Foundation of China （No.21673214）.
文摘A series of carbon nanotubes-supported K-Co-Mo catalysts were prepared by a sol-gel method combined with incipient wetness impregnation. The catalyst structures were characterized by X-ray diffraction, N2 adsorption-desorption, transmission electron microscopy and H2-TPD, and its catalytic performance toward the synthesis of higher alcohols from syngas was investigated. The as-prepared catalyst particles had a low crystallization degree and high dispersion on the outer and inner surface of CNTs. The uniform mesoporous structure of CNTs increased the diffusion rate of reactants and products, thus promoting the reaction conversion. Furthermore, the incorporation of CNTs support led to a high capability of hydrogen absorption and spillover and promoted the formation of alkyl group, which served as the key intermediate for the alcohol formation and carbon chain growth. Benefiting from these characteristics, the CNTs supported Mo-based catalyst showed the excellent catalytic performance for the higher alcohols synthesis as compared to the unsupported catalyst and activated carbon supported catalyst.
文摘A series of perovskite type oxides and supported Ag catalysts were prepared, and characterized by X ray diffraction (XRD) and X ray photoelectron spectroscopy (XPS). The catalytic activities of the catalysts as well as influencing factors on catalytic activity have been investigated for the simultaneous removal of NOx and diesel soot particulate. An increase in catalytic activity for the selective reduction of NOx was observed with Ag addition in these perovskite oxides, especially with 5% Ag loading. This catalyst could be a promising candidate of catalytic material for the simultaneous elimination of NOx and diesel soot.
基金the National Natural Science Foundation of China(20825310,20973011)the National Basic Research Program of China(973 Program,2011CB201400,2011CB808700)
文摘Au]Cel_xZrxO2 catalysts （x = 0-0.8） were prepared by a deposition-precipitation method using Cel_xZrxO2 nanoparticles as supports with variable Ce and Zr contents. Their structures were characterized by complimentary means such as X-ray diffraction, Raman, scanning trans- mission electron microscopy and X-ray photoelectron spectroscopy （XPS）. These Au catalysts possessed similar sizes and crystalline phases of Cel_xZrzO2 supports as well as similar sizes and oxidation states of Au nanoparticles. The oxidation state of Au nanoparticles was dominated by Au~ especially in CO oxidation. Their activities were examined in CO oxidation at different temperatures in the range of 303-333 K. The CO oxidation rates normalized per Au atoms increased with the increasing Ce contents, and reached the maximum value over Au/CeO2. Such change was in parallel with the change in the oxygen storage capacity values, i.e. the amounts of active oxygen species on Au/Cel_zZrzO2 catalysts. The excellent correlation between the two properties of the catalysts suggests that the intrinsic support effects on the CO oxidation rates is related to the effects on the adsorption and activation of O2 on Au/Cel_xZrxO2 catalysts. Such understanding on the support effects may be useful for designing more active Au catalysts, for example, by tuning the redox properties of oxide supports.
基金The project is supported by Guangdong Provincial Natural Science Foundation of China(030514)Science and Technology Plan of Guangdong Province(2004B33401006)
文摘Ni catalysts supported on various mixed oxides of Al2O3 with rare earth oxide and transitional metal oxides were synthesized. The studies focused on the measurement of the autothermal reforming of methane to hydrogen over Ni catalysts supported on the mixed oxide ZrxCe30-xAl70Oδ （x-=5, 10, 15）. The catalytic performance of Ni/Zr10Ce20Al70Oδ was better than that of other catalysts. XRD results showed that the addition of Zr to Ni/Ce30Al70Oδ prevented the formation of NiAl2O4 and facilitated the dispersion of NiO. Effects of CuO addition to Zr10Ce20Al70Oδ were also investigated. The activity of Ni catalyst supported on CuO-ZrO2-CeO2-Al2O3 was somewhat affected and the Ni/Cu5Zr10Ce20Al65Oδ showed the best catalytic performance with the highest CH4 conversion, yield of H2, selectivity for H2 and H2/CO production ratio in operation temperatures ranging from 650 to 750 ℃.
文摘The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR）, temperature-programmed desorption of hydrogen （H2-TPD） and activity evaluation, the physico-chemical and catalytic properties of the catalysts were investigated. Among the catalysts tested, the SiO2 supported nickel catalyst showed the highest activity and selectivity towards m-phenylenediamine, over which 97.3% m-dinitrobenzene conversion and 95.1% m-phenylenediamine yield were obtained at 373K under hydrogen pressure of 2.6MPa after reaction for 6 h when using ethanol as solvent. Although TiO2 and diatomite supported nickel catalysts also presented high activity, they had lower selectivity towards m-phenylenediamine. As for γ-Al2O3 and MgO supported catalysts were almost inactive for the object reaction. It was shown that both the activity and selectivity of the catalysts were strongly depended on the interaction between nickel and the support. The higher activities of Ni/SiO2, Ni/TiO2 and Ni/diatomite could be attributed to the weaker metal-support interaction, on which Ni species presented as crystallized Ni metal particles. On the other hand, there existed strong metal-support interaction in Ni/MgO and Ni γ-Al2O3, which causes these catalysts more difficult to be reduced and the availability of Ni active sites decreased, resulting in their low catalytic activity.
文摘Most of volatile organic compounds(VOCs)are harmful to the atmosphere and human health.Cata‐lytic combustion is an effective way to eliminate VOCs.The key issue is the availability of high per‐formance catalysts.Many catalysts including transition metal oxides,mixed metal oxides,and sup‐ported noble metals have been developed.Among these catalysts,the porous ones attract much attention.In this review,we focus on recent advances in the synthesis of ordered mesoporous and macroporous transition metal oxides,perovskites,and supported noble metal catalysts and their catalytic oxidation of VOCs.The porous catalysts outperformed their bulk counterparts.This excel‐lent catalytic performance was due to their high surface areas,high concentration of adsorbed oxy‐gen species,low temperature reducibility,strong interaction between noble metal and support and highly dispersed noble metal nanoparticles and unique porous structures.Catalytic oxidation of carbon monoxide over typical catalysts was also discussed.We made conclusive remarks and pro‐posed future work for the removal of VOCs.
基金financially supported by the National Natural Science Foundation of China (No. 51773178)
文摘Propylene slurry polymerization with a MgCl2-supported Ziegler-Natta catalyst containing internal electron donor was conducted after different durations of pre-contact of the catalyst with triethylaluminum cocatalyst. The number of active centers([C*]/[Ti])was determined by quenching the polymerization with 2-thiophenecarbonyl chloride and measuring sulfur content in the polymer. The pre-contact treatment caused selective deactivation of a part of active centers with low stereoselectivity and much lower activity in the initial stage of polymerization as compared with the polymerization run without the pre-contact stage. The active center concentration and polymerization activity decreased with prolonging of the pre-contact stage. The proportion of stereoselective active centers was increased by prolonging the pre-contact stage, so the isotacticity of produced polypropylene was enhanced. Release of active centers through catalyst particle fragmentation was significantly retarded, and the polymerization rate curve changed from decay type to induction type by the precontact treatment. In the induction period both non-stereoselective and stereoselective active centers were released and activated, resulting in gradual reduction of the polymer’s isotacticity in the first 5-10 min of polymerization. Selective deactivation of non-stereoselective active centers also took place in propylene polymerization using the catalyst without pre-contacting with the cocatalyst. In this case, the polymerization rate decayed with time after a short induction period of 2-5 min. Over reduction of the active center precursors with low stereoselectivity by triethylaluminum was considered as the reason for their deactivation during the pre-contact or the polymerization processes.
