Ceria(CeO2)supports,synthesized by hydrothermal treatment with different synthesis time(CeO2-X h,where X is the synthesis time in h)in the presence of the surfactant cetyltrimethyl ammonium bromide,were used as suppor...Ceria(CeO2)supports,synthesized by hydrothermal treatment with different synthesis time(CeO2-X h,where X is the synthesis time in h)in the presence of the surfactant cetyltrimethyl ammonium bromide,were used as supports for gold(Au)catalysts.The synthesis time significantly affects the morphological structure and crystallite size of CeO2,where CeO2-2 h has the smallest crystallite size with coexisting nanorods and nanoparticles.Transmission electron microscopy analysis confirms the morphology of CeO2 with distinctive(110),(100)and(111)planes,in agreement with interplanar spacings of 0.19,0,27 and 0.31,respectively.However,the morphology of CeO2-8 h and CeO2-48 h is mainly a truncated octahedral with crystal planes(111)and(100)accompanied by an interplanar spacing of 0.31 and0.27 nm,respectively.The CeO2-X h supports and those with a 3 wt%Au loading(Au/CeO2-X h)were investigated in the oxidative steam reforming of methanol at temperatures between 200 and 400℃.The Au/CeO2-2 h gave the highest methanol conversion level and hydrogen yield at a low temperature of 250℃.This superior catalytic performance results from the good interaction between the metal and support and the well-distributed Au species on the CeO2 support.展开更多
The COPZr-2 catalyst, which was prepared in our prophase research, showed good catalytic performance in methanol steam reforming reaction. In this article, the best one was chosen as an example to study the reaction k...The COPZr-2 catalyst, which was prepared in our prophase research, showed good catalytic performance in methanol steam reforming reaction. In this article, the best one was chosen as an example to study the reaction kinetics of methanol steam reforming over this type of catalyst. First, the effects of methanol conversion to outlet CO2 and methanol conversion to outlet CO on methanol pseudo contact time W/FMeOH were investigated. Then by applying the reaction route that methanol direct reforming （DR） and methanol decomposition （DE） were carried out in parallel, the reaction kinetic model with power function type was established. And the parameters for the model were estimated using a non-linear regression program which computed weighted least squares of the defined objects function. Finally, the kinetic model passed the correlation test and the F-test.展开更多
For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a...For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a promising photocatalyst for the generation of hydrogen.To improve the separation of photogenerated charge,porous nanosheet g-C_(3)N_(4)was modified with Pt nanoclusters(Pt/g-C_(3)N_(4))through impregnation and following photo-induced reduction.This catalyst showed excellent photocatalytic activity of water reforming of methanol fo r hydrogen production with a 17.12 mmol·g^(-1)·h^(-1)rate at room temperature,which was 311 times higher than that of the unmodified g-C_(3)N_(4).The strong interactions of Pt-N in Pt/g-C_(3)N_(4)constructed effective electron transfer channels to promote the separation of photogenerated electrons and holes effectively.In addition,in-situ infrared spectroscopy was used to investigate the intermediates of the hydrogen production reaction,which proved that methanol and water eventually turn into H_(2)and CO_(2)via formaldehyde and formate.This study provides insights for understanding the photocatalytic hydrogen production in the water reforming of methanol.展开更多
The sorption-enhanced steam reforming process of methanol（SESRP-Me OH） to produce high-purity H2 was thermodynamically and experimentally studied.Thermodynamic calculations showed that at a CO2 adsorption ratio of 9...The sorption-enhanced steam reforming process of methanol（SESRP-Me OH） to produce high-purity H2 was thermodynamically and experimentally studied.Thermodynamic calculations showed that at a CO2 adsorption ratio of 95%,product gas contains 98.36% H2,32.8 ppm CO under temperature of 130°C and steam-to-methanol（S/M） molar ratio of 2.However,without adsorption-enhanced,the product gas contains nearly 74.99% H2 with 24.96% CO2 and 525 ppm CO.To verify the thermodynamic calculation results,experiments were performed in a fixed-bed reactor loaded with commercial Cu O/Zn O/Al2O3 methanol reforming catalyst and 22% K2CO3-promoted hydrotalcite as CO2 adsorbent.Experimental results showed that 99.61% H2 could be obtained by SESRP-Me OH at reaction temperature of 230°C and S/M of 2.Under the same CH3 OH conversion,the reaction temperature decreased by almost 50°C and H2 concentration increased of more than 20%using SESRP-Me OH compared with solely steam reforming of methanol.The characterization of the adsorbent and catalyst showed that the adsorbent showed good stability while the catalyst was seriously sintered under the high regeneration temperature of the adsorbent.展开更多
In order to efficiently produce H_(2),conventional methanol‐water thermocatalytic(TC)reforming requires a very high temperature due to high Gibbs free energy,while the energy conversion efficiency of methanol‐water ...In order to efficiently produce H_(2),conventional methanol‐water thermocatalytic(TC)reforming requires a very high temperature due to high Gibbs free energy,while the energy conversion efficiency of methanol‐water photocatalytic(PC)reforming is far from satisfaction because of the kinetic limitation.To address these issues,herein,we incorporate PC and TC processes together in a specially designed reactor and realize simultaneous photocatalytic/thermocatalytic(PC‐TC)reforming of methanol in an aqueous phase.Such a design facilitates the synergetic effect of the PC and TC process for H_(2) production due to a lower energy barrier and faster reaction kinetics.The methanol‐water reforming based on the optimized 0.05%Pt@TiO_(2) catalyst delivers an outstanding H_(2) production rate in the PC‐TC process(5.66μmol H_(2)·g^(‒1) catalyst·s^(‒1)),which is about 3 and 7 times than those of the TC process(1.89μmol H_(2)·g^(‒1) catalyst·s^(‒1))and the PC process(0.80μmol H_(2)·g^(‒1) catalyst·s^(‒1)),respectively.Isotope tracer experiments,active intermediate trapping experiments,and theoretical calculations demonstrate that the photo‐generated holes and hydroxyl radicals could enhance the methanol dehydrogenation,water molecule splitting,and water‐gas shift reaction,while high temperature accelerates reaction kinetics.The proposed PC‐TC reforming of methanol for hydrogen production can be a promising technology to solve the energy and environmental issue in the closed‐loop hydrogen economy in the near future.展开更多
Cu/ZnAlO catalysts derived from hydroxycarbonate precursors containinghydrotalcite-like layered double hydroxides (LDHs) were studied. The influence on the performanceof the catalysts was also studied when the Al in t...Cu/ZnAlO catalysts derived from hydroxycarbonate precursors containinghydrotalcite-like layered double hydroxides (LDHs) were studied. The influence on the performanceof the catalysts was also studied when the Al in the Cu/ZnAlO catalyst was partly or completelyreplaced by Zr or Ce.展开更多
From the chemical catalysis viewpoint,the excellent performance of CNTs in adsorption-activation of H2 and in promoting spillover of adsorbed H-species is very attractive,in addition to their nanosize channels,sp2-C c...From the chemical catalysis viewpoint,the excellent performance of CNTs in adsorption-activation of H2 and in promoting spillover of adsorbed H-species is very attractive,in addition to their nanosize channels,sp2-C constructed surfaces,and high thermal/electrical conductivity.This review examines some recent progresses of CNTs as a novel support or promoter of catalysts for certain hydrogenation or dehydrogenation reactions,e.g.,hydrogenation-conversion of syngas to yield alcohols and decomposition or steam-reforming of methanol to generate H2,mainly based on recent work carried out in our laboratory.展开更多
A porous ceramic support is designed as a multi-functional independent catalyst layer for solid oxide fuel cells(SOFCs)running on liquid hydrocarbon fuel.The layer consists of a highly porous Ce_(0.9)Ca_(0.1)O_(2−δ)c...A porous ceramic support is designed as a multi-functional independent catalyst layer for solid oxide fuel cells(SOFCs)running on liquid hydrocarbon fuel.The layer consists of a highly porous Ce_(0.9)Ca_(0.1)O_(2−δ)ceramic backbone and active NiMo catalysts,which could be integrated into the conventional Ni metal containing the anode for internal reforming of the hydrocarbon fuel.Compared to conventional catalyst layers sintered on the anodes,this independent catalyst layer could be simply assembled on top of the anode without additional sintering,thereby avoiding the mismatch of the thermal expansion coefficient between the catalyst layer and the anode and improving stability of a single cell.Moreover,a current collector layer could be inserted between the catalyst and the anode to enhance current collection efficiency and electrochemical performance of the single cell.At 750℃,the independent catalyst layer displays high activity towards the catalytic decomposition of methanol,and the single cell could achieve the maximum power density of 400–500 mW·cm^(−2)in dry methanol.Furthermore,by employing the independent catalyst layer,the single cell offers additional in-situ catalyst regeneration capability under the methanol operation mode.Feeding 10 mL·min−1 air into an anode channel for 5 min is found to be effective to burn out carbon species in the catalyst layer,which reduces the degradation rate of the cell voltage by orders of magnitude from 2.6 to 0.024 mV·h−1 during the operation of 360 h in dry methanol.The results demonstrate the significance of the independent catalyst layer design for direct internal reforming methanol fuel cells.展开更多
The catalytic performances of methanol steam reforming reactions on CuZn(Zr)AIO catalysts were studied. When the ZrO2 promoter was added to a CuZnAIO catalyst, its methanol conversion, H2 production and H2 selectivity...The catalytic performances of methanol steam reforming reactions on CuZn(Zr)AIO catalysts were studied. When the ZrO2 promoter was added to a CuZnAIO catalyst, its methanol conversion, H2 production and H2 selectivity improved greatly. By using the (?)COPZr-2 catalyst as an example, which exhibited the best catalytic performance, the optimized reaction conditions were established to be: 250℃, 0.1 MPa, H2O/MeOH=1.3, WHSV=3.56 h-1, and without carrier gas. A 150 h stability test of the (?)COPZr-2 catalyst showed that the catalyst had good stability, as the methanol conversion and H2 production could be kept at 88% and 83% respectively. Moreover, outlet H2 and CO contents were>63% and 0.20%-0.31%, respectively.展开更多
基金Project supported by the Ratchadaphiseksomphot Endowment Fund,Chulalongkorn University(CU-GES-60-04-63-03)the Thammasat University Research Fund under the Research University Network Initiative(8/2560)
文摘Ceria(CeO2)supports,synthesized by hydrothermal treatment with different synthesis time(CeO2-X h,where X is the synthesis time in h)in the presence of the surfactant cetyltrimethyl ammonium bromide,were used as supports for gold(Au)catalysts.The synthesis time significantly affects the morphological structure and crystallite size of CeO2,where CeO2-2 h has the smallest crystallite size with coexisting nanorods and nanoparticles.Transmission electron microscopy analysis confirms the morphology of CeO2 with distinctive(110),(100)and(111)planes,in agreement with interplanar spacings of 0.19,0,27 and 0.31,respectively.However,the morphology of CeO2-8 h and CeO2-48 h is mainly a truncated octahedral with crystal planes(111)and(100)accompanied by an interplanar spacing of 0.31 and0.27 nm,respectively.The CeO2-X h supports and those with a 3 wt%Au loading(Au/CeO2-X h)were investigated in the oxidative steam reforming of methanol at temperatures between 200 and 400℃.The Au/CeO2-2 h gave the highest methanol conversion level and hydrogen yield at a low temperature of 250℃.This superior catalytic performance results from the good interaction between the metal and support and the well-distributed Au species on the CeO2 support.
基金Natural Science Foundation of Guangdong Province (05300127,06021469)Science and Technology Program of Guangdong Province (2005B10201053)
文摘The COPZr-2 catalyst, which was prepared in our prophase research, showed good catalytic performance in methanol steam reforming reaction. In this article, the best one was chosen as an example to study the reaction kinetics of methanol steam reforming over this type of catalyst. First, the effects of methanol conversion to outlet CO2 and methanol conversion to outlet CO on methanol pseudo contact time W/FMeOH were investigated. Then by applying the reaction route that methanol direct reforming （DR） and methanol decomposition （DE） were carried out in parallel, the reaction kinetic model with power function type was established. And the parameters for the model were estimated using a non-linear regression program which computed weighted least squares of the defined objects function. Finally, the kinetic model passed the correlation test and the F-test.
基金supported by the National Natural Science Foundation of China(51672081)the Program of Tri-three Talents Project of Hebei Province(China,A202110002)+1 种基金the Young Top Talents Fund Program of Higher Education Institutions of Heibei Province(BJ2020009)the Project of Science and Technology Innovation Team,Tangshan(20130203D)。
文摘For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a promising photocatalyst for the generation of hydrogen.To improve the separation of photogenerated charge,porous nanosheet g-C_(3)N_(4)was modified with Pt nanoclusters(Pt/g-C_(3)N_(4))through impregnation and following photo-induced reduction.This catalyst showed excellent photocatalytic activity of water reforming of methanol fo r hydrogen production with a 17.12 mmol·g^(-1)·h^(-1)rate at room temperature,which was 311 times higher than that of the unmodified g-C_(3)N_(4).The strong interactions of Pt-N in Pt/g-C_(3)N_(4)constructed effective electron transfer channels to promote the separation of photogenerated electrons and holes effectively.In addition,in-situ infrared spectroscopy was used to investigate the intermediates of the hydrogen production reaction,which proved that methanol and water eventually turn into H_(2)and CO_(2)via formaldehyde and formate.This study provides insights for understanding the photocatalytic hydrogen production in the water reforming of methanol.
文摘The sorption-enhanced steam reforming process of methanol（SESRP-Me OH） to produce high-purity H2 was thermodynamically and experimentally studied.Thermodynamic calculations showed that at a CO2 adsorption ratio of 95%,product gas contains 98.36% H2,32.8 ppm CO under temperature of 130°C and steam-to-methanol（S/M） molar ratio of 2.However,without adsorption-enhanced,the product gas contains nearly 74.99% H2 with 24.96% CO2 and 525 ppm CO.To verify the thermodynamic calculation results,experiments were performed in a fixed-bed reactor loaded with commercial Cu O/Zn O/Al2O3 methanol reforming catalyst and 22% K2CO3-promoted hydrotalcite as CO2 adsorbent.Experimental results showed that 99.61% H2 could be obtained by SESRP-Me OH at reaction temperature of 230°C and S/M of 2.Under the same CH3 OH conversion,the reaction temperature decreased by almost 50°C and H2 concentration increased of more than 20%using SESRP-Me OH compared with solely steam reforming of methanol.The characterization of the adsorbent and catalyst showed that the adsorbent showed good stability while the catalyst was seriously sintered under the high regeneration temperature of the adsorbent.
文摘In order to efficiently produce H_(2),conventional methanol‐water thermocatalytic(TC)reforming requires a very high temperature due to high Gibbs free energy,while the energy conversion efficiency of methanol‐water photocatalytic(PC)reforming is far from satisfaction because of the kinetic limitation.To address these issues,herein,we incorporate PC and TC processes together in a specially designed reactor and realize simultaneous photocatalytic/thermocatalytic(PC‐TC)reforming of methanol in an aqueous phase.Such a design facilitates the synergetic effect of the PC and TC process for H_(2) production due to a lower energy barrier and faster reaction kinetics.The methanol‐water reforming based on the optimized 0.05%Pt@TiO_(2) catalyst delivers an outstanding H_(2) production rate in the PC‐TC process(5.66μmol H_(2)·g^(‒1) catalyst·s^(‒1)),which is about 3 and 7 times than those of the TC process(1.89μmol H_(2)·g^(‒1) catalyst·s^(‒1))and the PC process(0.80μmol H_(2)·g^(‒1) catalyst·s^(‒1)),respectively.Isotope tracer experiments,active intermediate trapping experiments,and theoretical calculations demonstrate that the photo‐generated holes and hydroxyl radicals could enhance the methanol dehydrogenation,water molecule splitting,and water‐gas shift reaction,while high temperature accelerates reaction kinetics.The proposed PC‐TC reforming of methanol for hydrogen production can be a promising technology to solve the energy and environmental issue in the closed‐loop hydrogen economy in the near future.
基金Financial support from Guangdong Provincial Natural Science Foundation of China (000435), the Doctoral Program Foun- dation of the Ministry of Education (20010561003) Guangzhou Municipal Science and Technology project (2001J1-C0211).
文摘Cu/ZnAlO catalysts derived from hydroxycarbonate precursors containinghydrotalcite-like layered double hydroxides (LDHs) were studied. The influence on the performanceof the catalysts was also studied when the Al in the Cu/ZnAlO catalyst was partly or completelyreplaced by Zr or Ce.
基金supported by the National Basic Research Program of China(2011CBA00508)the National Natural Science Foundation of China(20923004)the Program for Changjiang Scholars and Innovative Research Team in University(IRT1036)
文摘From the chemical catalysis viewpoint,the excellent performance of CNTs in adsorption-activation of H2 and in promoting spillover of adsorbed H-species is very attractive,in addition to their nanosize channels,sp2-C constructed surfaces,and high thermal/electrical conductivity.This review examines some recent progresses of CNTs as a novel support or promoter of catalysts for certain hydrogenation or dehydrogenation reactions,e.g.,hydrogenation-conversion of syngas to yield alcohols and decomposition or steam-reforming of methanol to generate H2,mainly based on recent work carried out in our laboratory.
基金support from the National Natural Science Foundation of China(No.22005051)Guangdong Basic and Applied Basic Research Foundation(Nos.2019A1515110237 and 2022A1515012001)+3 种基金Young Creative Talents Project of the Guangdong Provincial Department of Education(No.2019KQNCX166)Innovation Research Project of University in Foshan City(No.2020XCC09).Grateful acknowledgements are extended to the National Natural Science Foundation of China(No.51872047)Key Project Plat Form Programs and Technology Innovation Team Project of Guangdong Provincial Department of Education(Nos.2019KZDXM039,2019GCZX002,and 2020KCXTD011)Guangdong Provincial Key Research and Development Plan(No.2020B090920001)。
文摘A porous ceramic support is designed as a multi-functional independent catalyst layer for solid oxide fuel cells(SOFCs)running on liquid hydrocarbon fuel.The layer consists of a highly porous Ce_(0.9)Ca_(0.1)O_(2−δ)ceramic backbone and active NiMo catalysts,which could be integrated into the conventional Ni metal containing the anode for internal reforming of the hydrocarbon fuel.Compared to conventional catalyst layers sintered on the anodes,this independent catalyst layer could be simply assembled on top of the anode without additional sintering,thereby avoiding the mismatch of the thermal expansion coefficient between the catalyst layer and the anode and improving stability of a single cell.Moreover,a current collector layer could be inserted between the catalyst and the anode to enhance current collection efficiency and electrochemical performance of the single cell.At 750℃,the independent catalyst layer displays high activity towards the catalytic decomposition of methanol,and the single cell could achieve the maximum power density of 400–500 mW·cm^(−2)in dry methanol.Furthermore,by employing the independent catalyst layer,the single cell offers additional in-situ catalyst regeneration capability under the methanol operation mode.Feeding 10 mL·min−1 air into an anode channel for 5 min is found to be effective to burn out carbon species in the catalyst layer,which reduces the degradation rate of the cell voltage by orders of magnitude from 2.6 to 0.024 mV·h−1 during the operation of 360 h in dry methanol.The results demonstrate the significance of the independent catalyst layer design for direct internal reforming methanol fuel cells.
基金This work is supported by the National Science Foundation of Guangdong Province(000435)Research Foundation for the Doctoral Program of Higher Education of China(20010561003),Science and Technology Program of Guangzhou(2001J1-C0211)
文摘The catalytic performances of methanol steam reforming reactions on CuZn(Zr)AIO catalysts were studied. When the ZrO2 promoter was added to a CuZnAIO catalyst, its methanol conversion, H2 production and H2 selectivity improved greatly. By using the (?)COPZr-2 catalyst as an example, which exhibited the best catalytic performance, the optimized reaction conditions were established to be: 250℃, 0.1 MPa, H2O/MeOH=1.3, WHSV=3.56 h-1, and without carrier gas. A 150 h stability test of the (?)COPZr-2 catalyst showed that the catalyst had good stability, as the methanol conversion and H2 production could be kept at 88% and 83% respectively. Moreover, outlet H2 and CO contents were>63% and 0.20%-0.31%, respectively.
