Oxygen reduction reaction over Pt-based catalyst is one of the most significant cathode reactions in fuel cells.However,low reserves and high price of Pt have motivated researchers worldwide seeking enhanced utilizati...Oxygen reduction reaction over Pt-based catalyst is one of the most significant cathode reactions in fuel cells.However,low reserves and high price of Pt have motivated researchers worldwide seeking enhanced utilization efficiency and durability by doping non-noble metals to form Pt-based alloy catalysts.Alloying Pt with Co has been recognized as one of the most effective approaches to achieve this goal.PtCo bimetal combination is one of the most promising candidates to synthesize highly efficient catalysts for oxygen reduction reaction(ORR)applications,owing to its relatively more suitable oxygen binding energy for four-electron transfer reactions.Recently,impressive strategies have been developed to fabricate more active and stable PtCo-based multimetallic alloys with tailorable size and morphology.This paper aims to summarize the most recent highlights on the study of the relationship between preparation strategies,morphologies,electroactivities of the PtCo-based catalyst at atomic level and further the relevant reaction mechanism.The challenges and opportunities on the further development of electrocatalysts for fuel cells are included to provide reference for the practical application.展开更多
Pyrolysis has the potential of transforming waste into valuable products. Pyrolytic carbon black (PCB) is one of the most important products resulting from the pyrolysis of used tires. One of the most significant appl...Pyrolysis has the potential of transforming waste into valuable products. Pyrolytic carbon black (PCB) is one of the most important products resulting from the pyrolysis of used tires. One of the most significant applica-tions of modified pyrolytic carbon black is its use as pigment for offset printing ink to obtain high added values. Inverse gas chromatography (IGC) results show that a large quantity of inorganic matters and carbonaceous deposit are removed by treating the pyrolytic carbon black with nitric acid solution. Plenty of active sites originally occu-pied by inorganic ash and coke are recovered. The surface energy of pyrolytic carbon black (TWPC)modified by titanate-coupling agent-especially the specific interaction γ sspdetermined by the specific probe molecule, tolu-ene-shows the strong interaction between the TWPC and the synthetic resins. The offset printing ink performance confirms the IGC prediction. And TWPC has the great potential of applications in printing ink industry as pigment.展开更多
Pyrolysis has the potential of transforming waste into recyclable products. Pyrolytic carbon black (PCB) is one of the most important products from the pyrolysis of used tires. Techniques for surface modifications of ...Pyrolysis has the potential of transforming waste into recyclable products. Pyrolytic carbon black (PCB) is one of the most important products from the pyrolysis of used tires. Techniques for surface modifications of PCB have been developed. One of the most significant applications for modified PCB is to reinforce the rubber matrix to obtain high added values. The transverse relaxation and the chain dynamics of vulcanized rubber networks with PCB and modified PCB were studied and compared with those of the commercial carbon blacks using selective 1H transverse relaxation (T2) experiments and dipolar correlation effect (DCE) experiments on the stimulated echo. Demineralization and coupling agent modification not only intensified the interactions between the modified PCB and the neighboring polyisoprene chains, but also increased the chemical cross-link density of the vulcanized rubber with modified PCB. The mechanical testing of the rubbers with different kinds of carbon blacks showed that the maximum strain of the rubber with modified PCB was improved greatly. The mechanical testing results confirmed the conclusion obtained by nuclear magnetic resonance (NMR). PCB modified by the demineralization and NDZ-105 titanate coupling agent could be used to replace the commercial semi-reinforcing carbon black.展开更多
Adipic acid is a dicarboxylic acid of great industrial importance,mainly used in the production of nylon-6,6 and polyurethane.The use of nitric acid as an oxidant in the industrial production of adipic acid poses sign...Adipic acid is a dicarboxylic acid of great industrial importance,mainly used in the production of nylon-6,6 and polyurethane.The use of nitric acid as an oxidant in the industrial production of adipic acid poses significant carbon footprint to the environment.Clean adipic acid synthesis methods using a heterogeneous catalyst with H2O2 as oxidant and water as solvent have potential advantages of low catalyst cost,easy synthesis and recovery,cleanness and environmental protection.In this work,hexagonal mesoporous silicate materials were synthesized by a sol–gel method and evaluated for cyclohexanol/cyclohexanone oxidation to adipic acid.The physical and chemical properties of Fe-HMS were characterized by XRD,HR-TEM,BET and UV–Vis.The experimental results showed that Fe-HMS materials show pore sizes ranging from 2–3 nm.W-and Mo-based polyoxometalates were also evaluated and compared to the Fe-based HMS catalysts.To improve the adipic acid yield,the influence of the transition metal as well as the effect of metal loading,reaction temperature and catalyst amount on the catalytic performances of Fe-HMS have been investigated in details.When Si/Fe atomic ratio=100,Fe-HMS catalyst shows the highest activity,with a cyclohexanone conversion of 92.3%and adipic acid selectivity of 29.4%.The reaction pathway of cyclohexanone oxidation was further proposed based on experimental data.展开更多
Recently, Fischer-Tropsch synthesis (FTS) has become an interesting technology because of its potential role in producing biofuels via Biomass- to-Liquids (BTL) processes. In Fischer-Tropsch (FT) section, biomas...Recently, Fischer-Tropsch synthesis (FTS) has become an interesting technology because of its potential role in producing biofuels via Biomass- to-Liquids (BTL) processes. In Fischer-Tropsch (FT) section, biomass-derived syngas, mainly composed of a mixture of carbon monoxide (CO) and hydrogen (H2), is converted into various forms of hydrocarbon products over a catalyst at specified temperature and pressure. Fixed-bed reactors are typically used for these processes as conventional FT reactors. The fixed-bed or packed-bed type reactor has its drawbacks, which are heat transfer limitation, i.e. a hot spot problem involved highly exothermic characteristics of FT reaction, and mass transfer limitation due to the condensation of liquid hydrocarbon products occurred on catalyst surface. This work is initiated to develop a new chemical reactor design in which a better distribution of gaseous reactants and hydrocarbon products could be achieved, and led to higher throughput and conversion. The main goal of the research is the enhancement of a fixed-bed reactor, focusing on the application of KenicsTM static mixer insertion in the tubular packed-bed reactor. Two FTS experiments were carried out using two reactors i.e., with and without static mixer insertion within catalytic beds. The modeled syngas used was a mixed gas composed of H2/CO in 2 : 1 molar ratio that was fed at the rate of 30 mL(STP)·min^- 1 (GHSV ≈ 136 mL·gcat^-1 ·h^-1) into the fixed Ru supported aluminum catalyst bed of weight 13.3 g. The reaction was carried out at 180 ℃ and atmospheric pressure continuously for 36 h for both experiments. Both transient and steady-state conversions (in terms of time on stream) were reported. The results revealed that the steady-state CO conversion for the case using the static mixer was approximately 3.5 times higher than that of the case without static mixer. In both cases, the values of chain growth probability of hydrocarbon products (α) for Fischer-Tropsch synthesis were 0.92 and 0.89 for the case with and without static mixer, respectively.展开更多
Proton exchange membrane fuel cell and direct methanol fuel cells have gained more attention due to high-energy density,remarkable conversion efficiency,and low emission.However,their widely practical application was ...Proton exchange membrane fuel cell and direct methanol fuel cells have gained more attention due to high-energy density,remarkable conversion efficiency,and low emission.However,their widely practical application was hindered by the high usage,limited sources,and high price of Pt catalysts.To achieve more cost-effective catalytic systems,PtCu-based multi-metallic nanoparticles are highly efficient for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR).The incorporation of non-noble Cu metal can alter the properties of hybrids by forming new facets,planes,edges to promote the cleavage or formation of chemical bonds in catalytic reaction.This is a rapid growing area with numerous contributions from the interdisciplinary areas of nanocatalysis.This paper has summarized the recent progress in the past two years,in synthesizing PtCu-based alloys with various composition and morphologies,and critically discussed the effect of the catalyst preparation method,metal precursor,surfactant,reductant and heating temperature on nanostructure and electronic configuration.The important role of the composition,size,and morphology of PtCu bimetallic catalysts for electro oxidation reactions has been further established for structure-dependency studies.The challenges and perspectives of nanocatalysts for ORR and MOR discussed in this work is to provide further insights into rational design for cost-effective materials for energy.展开更多
Terminal olefins are important building blocks for the industry of biofuels,oligomers,and lubricants production.The industrial processes for production of olefins involving oligomerization of ethylene or cracking of p...Terminal olefins are important building blocks for the industry of biofuels,oligomers,and lubricants production.The industrial processes for production of olefins involving oligomerization of ethylene or cracking of petrochemical waxes have several flaws including low yield and high cost in product separation.Cross-metathesis of bio-derived unsaturated fatty esters and olefins with ethylene(ethenolysis),allows the conversion of sustainable waste biomass to various renewable olefins with much safer,less toxic,sustainable,and zero-CO_(2) emission processes.To our best knowledge,however,a comprehensive summary of key advances in this field(since 2017)is yet to be available,particularly on molecular features of homogeneous and heterogeneous catalysts.This paper presents a critical review on molecular structures of metal complex and oxide catalysts for ethenolysis of olefins and oleochemicals.The influence of cationic centers,coordination conditions,nature of ligands,operating conditions on catalyst performances will be systematically discussed along with relevant reaction mechanism.The key challenges for rational design of coordinated cationic hybrids have been summarized,which will provide insights to technological advancement of large-scale production of oleochemical-derived olefins.展开更多
基金supported by the National Natural Science Foundation of China(22008262)Natural Science Foundation of Shandong Province(ZR2020QB187).
文摘Oxygen reduction reaction over Pt-based catalyst is one of the most significant cathode reactions in fuel cells.However,low reserves and high price of Pt have motivated researchers worldwide seeking enhanced utilization efficiency and durability by doping non-noble metals to form Pt-based alloy catalysts.Alloying Pt with Co has been recognized as one of the most effective approaches to achieve this goal.PtCo bimetal combination is one of the most promising candidates to synthesize highly efficient catalysts for oxygen reduction reaction(ORR)applications,owing to its relatively more suitable oxygen binding energy for four-electron transfer reactions.Recently,impressive strategies have been developed to fabricate more active and stable PtCo-based multimetallic alloys with tailorable size and morphology.This paper aims to summarize the most recent highlights on the study of the relationship between preparation strategies,morphologies,electroactivities of the PtCo-based catalyst at atomic level and further the relevant reaction mechanism.The challenges and opportunities on the further development of electrocatalysts for fuel cells are included to provide reference for the practical application.
基金Supported by the National Natural Science Foundation of China (No.20176051) and the Key Natural Science Foundation ofChina (No.20490205).
文摘Pyrolysis has the potential of transforming waste into valuable products. Pyrolytic carbon black (PCB) is one of the most important products resulting from the pyrolysis of used tires. One of the most significant applica-tions of modified pyrolytic carbon black is its use as pigment for offset printing ink to obtain high added values. Inverse gas chromatography (IGC) results show that a large quantity of inorganic matters and carbonaceous deposit are removed by treating the pyrolytic carbon black with nitric acid solution. Plenty of active sites originally occu-pied by inorganic ash and coke are recovered. The surface energy of pyrolytic carbon black (TWPC)modified by titanate-coupling agent-especially the specific interaction γ sspdetermined by the specific probe molecule, tolu-ene-shows the strong interaction between the TWPC and the synthetic resins. The offset printing ink performance confirms the IGC prediction. And TWPC has the great potential of applications in printing ink industry as pigment.
基金Project supported by the National Natural Science Foundation of China (Nos. 20490200 and 20176051), and the Project Based Per-sonnel Exchange Program with the China Scholarship Council and the German Academic Exchange Service
文摘Pyrolysis has the potential of transforming waste into recyclable products. Pyrolytic carbon black (PCB) is one of the most important products from the pyrolysis of used tires. Techniques for surface modifications of PCB have been developed. One of the most significant applications for modified PCB is to reinforce the rubber matrix to obtain high added values. The transverse relaxation and the chain dynamics of vulcanized rubber networks with PCB and modified PCB were studied and compared with those of the commercial carbon blacks using selective 1H transverse relaxation (T2) experiments and dipolar correlation effect (DCE) experiments on the stimulated echo. Demineralization and coupling agent modification not only intensified the interactions between the modified PCB and the neighboring polyisoprene chains, but also increased the chemical cross-link density of the vulcanized rubber with modified PCB. The mechanical testing of the rubbers with different kinds of carbon blacks showed that the maximum strain of the rubber with modified PCB was improved greatly. The mechanical testing results confirmed the conclusion obtained by nuclear magnetic resonance (NMR). PCB modified by the demineralization and NDZ-105 titanate coupling agent could be used to replace the commercial semi-reinforcing carbon black.
基金supported by the National Natural Science Foundation(21706290)Natural Science Foundation of Shandong Province(ZR2017MB004,ZR2017BB007)+5 种基金Postdoctoral Research Funding of Shandong Province(201703016)Fundamental Research Funding of Qingdao(17-1-1-67-jch,17-1-1-80-jch)Qingdao Postdoctoral Research Funding(BY20170210)“the Fundamental Research Funds for the Central Universities”(18CX02145A,17CX02017A)new faculty start-up funding from China University of Petroleum(YJ201601058)China Postdoctoral Science Foundation(2017M612374)。
文摘Adipic acid is a dicarboxylic acid of great industrial importance,mainly used in the production of nylon-6,6 and polyurethane.The use of nitric acid as an oxidant in the industrial production of adipic acid poses significant carbon footprint to the environment.Clean adipic acid synthesis methods using a heterogeneous catalyst with H2O2 as oxidant and water as solvent have potential advantages of low catalyst cost,easy synthesis and recovery,cleanness and environmental protection.In this work,hexagonal mesoporous silicate materials were synthesized by a sol–gel method and evaluated for cyclohexanol/cyclohexanone oxidation to adipic acid.The physical and chemical properties of Fe-HMS were characterized by XRD,HR-TEM,BET and UV–Vis.The experimental results showed that Fe-HMS materials show pore sizes ranging from 2–3 nm.W-and Mo-based polyoxometalates were also evaluated and compared to the Fe-based HMS catalysts.To improve the adipic acid yield,the influence of the transition metal as well as the effect of metal loading,reaction temperature and catalyst amount on the catalytic performances of Fe-HMS have been investigated in details.When Si/Fe atomic ratio=100,Fe-HMS catalyst shows the highest activity,with a cyclohexanone conversion of 92.3%and adipic acid selectivity of 29.4%.The reaction pathway of cyclohexanone oxidation was further proposed based on experimental data.
基金supported by the project of the National Science and Technology Development Agency (NSTDA),Thailand
文摘Recently, Fischer-Tropsch synthesis (FTS) has become an interesting technology because of its potential role in producing biofuels via Biomass- to-Liquids (BTL) processes. In Fischer-Tropsch (FT) section, biomass-derived syngas, mainly composed of a mixture of carbon monoxide (CO) and hydrogen (H2), is converted into various forms of hydrocarbon products over a catalyst at specified temperature and pressure. Fixed-bed reactors are typically used for these processes as conventional FT reactors. The fixed-bed or packed-bed type reactor has its drawbacks, which are heat transfer limitation, i.e. a hot spot problem involved highly exothermic characteristics of FT reaction, and mass transfer limitation due to the condensation of liquid hydrocarbon products occurred on catalyst surface. This work is initiated to develop a new chemical reactor design in which a better distribution of gaseous reactants and hydrocarbon products could be achieved, and led to higher throughput and conversion. The main goal of the research is the enhancement of a fixed-bed reactor, focusing on the application of KenicsTM static mixer insertion in the tubular packed-bed reactor. Two FTS experiments were carried out using two reactors i.e., with and without static mixer insertion within catalytic beds. The modeled syngas used was a mixed gas composed of H2/CO in 2 : 1 molar ratio that was fed at the rate of 30 mL(STP)·min^- 1 (GHSV ≈ 136 mL·gcat^-1 ·h^-1) into the fixed Ru supported aluminum catalyst bed of weight 13.3 g. The reaction was carried out at 180 ℃ and atmospheric pressure continuously for 36 h for both experiments. Both transient and steady-state conversions (in terms of time on stream) were reported. The results revealed that the steady-state CO conversion for the case using the static mixer was approximately 3.5 times higher than that of the case without static mixer. In both cases, the values of chain growth probability of hydrocarbon products (α) for Fischer-Tropsch synthesis were 0.92 and 0.89 for the case with and without static mixer, respectively.
基金supported by the National Natural Science Foundation(22078365,22008262)the Natural Science Foundation of Shandong Province(ZR2020QB187)+3 种基金the Postdoctoral Research Fun ding of Shand ong Province(201703016)the Qingdao Postdoctoral Research Funding(BY20170210)the"Fundamental Research Funds for the Central Universities"and"the Development Fund of State Key Laboratory of Heavy Oil Processing"(18CX02145A,17CX02017A,20CX02204A)the new faculty start-up funding from the China University of Petroleum(YJ201601058).
文摘Proton exchange membrane fuel cell and direct methanol fuel cells have gained more attention due to high-energy density,remarkable conversion efficiency,and low emission.However,their widely practical application was hindered by the high usage,limited sources,and high price of Pt catalysts.To achieve more cost-effective catalytic systems,PtCu-based multi-metallic nanoparticles are highly efficient for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR).The incorporation of non-noble Cu metal can alter the properties of hybrids by forming new facets,planes,edges to promote the cleavage or formation of chemical bonds in catalytic reaction.This is a rapid growing area with numerous contributions from the interdisciplinary areas of nanocatalysis.This paper has summarized the recent progress in the past two years,in synthesizing PtCu-based alloys with various composition and morphologies,and critically discussed the effect of the catalyst preparation method,metal precursor,surfactant,reductant and heating temperature on nanostructure and electronic configuration.The important role of the composition,size,and morphology of PtCu bimetallic catalysts for electro oxidation reactions has been further established for structure-dependency studies.The challenges and perspectives of nanocatalysts for ORR and MOR discussed in this work is to provide further insights into rational design for cost-effective materials for energy.
基金supported by the National Natural Science Foundation of China(22078365,22008262)Natural Science Foundation of Shandong Province(ZR2020QB187)+3 种基金Postdoctoral Research Funding of Shandong Province(201703016)Qingdao Postdoctoral Research Funding(BY20170210)the Development Fund of State Key Laboratory of Heavy Oil Processing(20CX02204A)new faculty start-up funding from the China University of Petroleum(YJ201601058)。
文摘Terminal olefins are important building blocks for the industry of biofuels,oligomers,and lubricants production.The industrial processes for production of olefins involving oligomerization of ethylene or cracking of petrochemical waxes have several flaws including low yield and high cost in product separation.Cross-metathesis of bio-derived unsaturated fatty esters and olefins with ethylene(ethenolysis),allows the conversion of sustainable waste biomass to various renewable olefins with much safer,less toxic,sustainable,and zero-CO_(2) emission processes.To our best knowledge,however,a comprehensive summary of key advances in this field(since 2017)is yet to be available,particularly on molecular features of homogeneous and heterogeneous catalysts.This paper presents a critical review on molecular structures of metal complex and oxide catalysts for ethenolysis of olefins and oleochemicals.The influence of cationic centers,coordination conditions,nature of ligands,operating conditions on catalyst performances will be systematically discussed along with relevant reaction mechanism.The key challenges for rational design of coordinated cationic hybrids have been summarized,which will provide insights to technological advancement of large-scale production of oleochemical-derived olefins.