Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still fac...Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still face relatively low NH3yield rate and poor stability. We present here a core-shell heterostructure comprising cobalt oxide anchored on copper oxide nanowire arrays(CuO NWAs@Co_(3)O_(4)) for efficient NRA. The CuO NWAs@Co_(3)O_(4)demonstrates significantly enhanced NRA performance in alkaline media in comparison with plain CuO NWAs and Co_(3)O_(4)flocs. Especially, at-0.23 V vs. RHE, NH_(3) yield rate of the CuO NWAs@Co_(3)O_(4)reaches 1.915 mmol h^(-1)cm^(-2),much higher than those of CuO NWAs(1.472 mmol h^(-1)cm^(-2)), Co_(3)O_(4)flocs(1.222 mmol h^(-1)cm^(-2)) and recent reported Cu-based catalysts.It is proposed that the synergetic effects of the heterostructure combing atom hydrogen adsorption and nitrate reduction lead to the enhanced NRA performance.展开更多
The solid structures and thermostabilities of Cu-Fe-O and Cu-Fe-Ce-O supported on alumina were studied by XRD, ESR, Mossbauer and TPR techniques. The studies indicate that there are Fe2CuO4, CuO and alpha-Fe2O3 phases...The solid structures and thermostabilities of Cu-Fe-O and Cu-Fe-Ce-O supported on alumina were studied by XRD, ESR, Mossbauer and TPR techniques. The studies indicate that there are Fe2CuO4, CuO and alpha-Fe2O3 phases in Cu-Fe-O with the granula of less than 13 nm. With the catalyst pretreatment temperature rising, the crystallite of Fe2CuO4 in the catalysts grows up and that of CuO disappears gradually. The presence of Ce leads to the increase of Cu2+ concentration, inhibits the crystal growth of CuO and Fe2CuO4 in the catalyst except that of Fe2O3, and eliminates the difference for reductive reaction of oxygen in Fe-O and Cu-O. At 800 degrees C, the crystal growth of Fe2O3 in Cu-Fe-Ce-O is slower than that in Cu-Fe-O, i.e., CeO2 in Cu-Fe-Ce-O inhibits the growth of Fe2O3 phase effectively, and enhances the thermostability of catalysts so as to avoid the sintering of active elements in catalysts. CeO2 promotes the reducibility of catalysts at lower temperature.展开更多
Cobalt-Boron oxides containing catalyst CoO·B2O3 (CoB2O4) are synthesized for hydrogen generation by catalytic reforming of basic solution of sodium hypophosphite (NaH2PO2) and identified by chemical and X-ray an...Cobalt-Boron oxides containing catalyst CoO·B2O3 (CoB2O4) are synthesized for hydrogen generation by catalytic reforming of basic solution of sodium hypophosphite (NaH2PO2) and identified by chemical and X-ray analysis. Reforming is performed in temperature range of 30°C - 80°C. Reaction rate constants at each value of temperature (k30°C = 8.53 × 10?4 s?1;k40°C = 1.62 × 10?4 s??;k50°C = 3.06 × 10?3 s?1;k60°C = 5.06 × 10?3 s?1;k80°C = 1.39 × 10?2 s?1), temperature coefficient of rate of chemical reaction (γ = 0.917) and activation energy (EA = 49.59 kJ·mol?1) are calculated.展开更多
A sulphuric acid bake–leach method for the treatment of mixed copper-cobalt oxide minerals was investigated as an alternative to the reductive leaching method. Sulphuric acid bake-leach process of the mixed copper-co...A sulphuric acid bake–leach method for the treatment of mixed copper-cobalt oxide minerals was investigated as an alternative to the reductive leaching method. Sulphuric acid bake-leach process of the mixed copper-cobalt oxide ore was carried out by mixing the sample with sulphuric acid followed by baking of the mixture in a muffle furnace. Baking tests were conducted at different conditions such as temperature, time, and varying amounts of acid. The reacted samples were then subjected to water leaching at room temperature to determine the leachability of copper and cobalt from the baked material. The dissolutions of copper and cobalt were dependent on acid concentration with cobalt showing more sensitivity to the amount of acid. Both copper and cobalt were extracted from the baked material within short leaching times and without the addition of reducing agents. The outcome of this work has shown that the sulphuric acid bake-leach process is a possible alternative to the reductive leaching method for copper-cobalt oxide ores.展开更多
A microreactor system was used to study the catalytic reaction of NO+CO→1/2 N_2+CO_2 over Cu,Fe, Mn,Cr,and Ce oxides supported on alumina,and the effect of adding Ce in supported Cu-M-O(M=Mn,Fe and Cr) catalysts on t...A microreactor system was used to study the catalytic reaction of NO+CO→1/2 N_2+CO_2 over Cu,Fe, Mn,Cr,and Ce oxides supported on alumina,and the effect of adding Ce in supported Cu-M-O(M=Mn,Fe and Cr) catalysts on their catalytic activities for the topic reaction and the concentration of N_2O produced.It was found that the catalytic activity order of the single-element oxide is:CuO>Fe_2O_3≈Cr_2O_3> MnO_2>CeO_2>NiO.Cu-Mn-O is more active than CuO,and Cu-Fe-O is more active than Cu-Mn-O and Cu-Cr-O for NO+CO reaction.This study shows that the addition of Ce in supported Cu-M-O can promote their catalytic activities Jot the topic reaction,which makes the reaction of 2NO+CO→N_2O+CO_2 fast,and N_2O is an intermediate compound produced during NO+CO reaction.展开更多
A series of alumina supported cobalt oxide based catalysts doped with noble metals such as ruthenium and platinum were prepared by wet impregnation method.The variables studied were difference ratio and calcination te...A series of alumina supported cobalt oxide based catalysts doped with noble metals such as ruthenium and platinum were prepared by wet impregnation method.The variables studied were difference ratio and calcination temperatures.Pt/Co(10∶90)/Al2O3 catalyst calcined at 700 ℃ was found to be the best catalyst which able to convert 70.10% of CO2 into methane with 47% of CH4 formation at maximum temperature studied of 400 ℃.X-ray diffraction analysis showed that this catalyst possessed the active site Co3O4 in face-centered cubic and PtO2 in the orthorhombic phase with Al2O3 existed in the cubic phase.According to the FESEM micrographs,both fresh and spent Pt/Co(10∶90)/Al2O3 catalysts displayed small particle size with undefined shape.Nitrogen Adsorption analysis showed that 5.50% reduction of the total surface area for the spent Pt/Co(10∶90)/Al2O3 catalyst.Meanwhile,Energy Dispersive X-ray analysis(EDX) indicated that Co and Pt were reduced by 0.74% and 0.14% respectively on the spent Pt/Co(10∶90)/Al2O3catalyst.Characterization using FT-IR and TGA-DTA analysis revealed the existence of residual nitrate and hydroxyl compounds on the Pt/Co(10∶90)/Al2O3 catalyst.展开更多
Supported Cu catalysts for low-temperature CO oxidation were prepared by solvated metal atom impregnation (SMAI). X-ray photoelectron spectroscopy (XPS) investigations indicated that the copper in all the samples was...Supported Cu catalysts for low-temperature CO oxidation were prepared by solvated metal atom impregnation (SMAI). X-ray photoelectron spectroscopy (XPS) investigations indicated that the copper in all the samples was in a metallic state. XRD measurements showed that the mean diameters of Cu particles prepared by SMAI were small. Catalytical tests showed that the SMAI catalyst had high CO oxidation activity.展开更多
Metal-organic framework(MOF) material MIL-53(A1) with high thermal stability was prepared by a solvothermal method,serving as a support material of cerium doped copper catalyst(Ce-Cu)/MIL-53(A1) material for C...Metal-organic framework(MOF) material MIL-53(A1) with high thermal stability was prepared by a solvothermal method,serving as a support material of cerium doped copper catalyst(Ce-Cu)/MIL-53(A1) material for CO oxidation with high catalytic activity.The catalytic performance between the(CuCe)/MIL-53(A1) and the Cu/MIL-53(A1) catalytic material was compared to understand the catalytic behavior of the catalysts.The catalysts were characterized by thermogravimetric-differential scanning calorimetry(TGDSC),N2 adsorption- desorption,X-ray diffraction(XRD),and transmission electron microscopy(TEM).The characterization results showed that MIL-53(A1) had good stability and high surface areas,the(Ce-Cu)nanoparticles on the MIL-53(A1) support was uniform.Therefore,the heterogeneous catalytic composite materials(Ce-Cu)/MIL-53(A1) catalyst exhibited much higher activity than that of the Cu/MIL- 53(A1) catalyst in CO oxidation test,with 100%conversion at 80 ℃.The results reveal that(Cu-Ce)/MIL-53(A1) is the suitable candidate for achieving low temperature and higher activity CO oxidation catalyst of MOFs.展开更多
Several researches have been reported about the characteristic of β-Ga_2O_3 nanowires which was synthesized on nickel oxide particle.But indeed,recent researches about synthesis of β-Ga_2O_3 nanowires on oxide-assis...Several researches have been reported about the characteristic of β-Ga_2O_3 nanowires which was synthesized on nickel oxide particle.But indeed,recent researches about synthesis of β-Ga_2O_3 nanowires on oxide-assisted transition metal are limited to nickel or cobalt oxide catalyst.In this work,Gallium oxide(β-Ga_2O_3)nanowires were synthesized by a simple thermal evaporation method from gallium powder in the range of 700-1000℃ using the iron,nickel,copper,cobalt and zinc oxide as a catalyst,respectively.The β-Ga_2O_3 nanowires with single crystalline without defects were successfully synthesized at the reaction temperature of 850,900 and 950℃ in all the catalysts.But optimum experimental condition in synthesis of nanowires varied with the kind of catalyst.As increasing synthesis temperature,the morphology of gallium oxide nanowires changed from nanowires to nanorods,and its diameter increased.From these results,we could be proposed that the growth mechanism of β-Ga_2O_3 nanowires was changed with synthesis temperature of nanowires.Microstructure and morphology of Synthesized nanowire was characterized by HR-TEM,FE-SEM,EDX and XRD.展开更多
Four perovskite-type complex oxides (LaNiO_3, La_2NiO_4, LaCoO_3 andLa_2CoO_4) were successfully prepared using two sol-gel methods, the Pechini method (PC) and thecitric acid complexing method (CC). The catalysts wer...Four perovskite-type complex oxides (LaNiO_3, La_2NiO_4, LaCoO_3 andLa_2CoO_4) were successfully prepared using two sol-gel methods, the Pechini method (PC) and thecitric acid complexing method (CC). The catalysts were characterized by XRD and TPR. Afterreduction, the activity of the catalysts in the CO_2 reforming of methane was tested. Ni-basedcatalysts from La_2NiO_4 precursors were the most active and stable catalyst after calcination above850 ℃, which gave a methane conversion of 0.025 mmol/(g·s) for those prepared by the PC methodand 0.020 mmol/(g·s) by the CC method. It was proposed that the well-defined structure and lowerreducibility is responsible for the unusual catalytic behavior observed over the pre-reducedLa2NiO_4 catalyst.展开更多
We have studied the reaction mechanism of CO oxidation on the Cu13 cluster via density functional theory. There are two main reaction pathways to be considered: Eley-Rideal(ER) and Langmuir-Hinshelwood(LH) mechan...We have studied the reaction mechanism of CO oxidation on the Cu13 cluster via density functional theory. There are two main reaction pathways to be considered: Eley-Rideal(ER) and Langmuir-Hinshelwood(LH) mechanisms, respectively. According to these two main reaction mechanisms, we have obtained five reaction pathways for the first CO oxidation(denoted as RER1,RER2, RLH1, RLH2 and RLH3, respectively): RER1 is COgas + O2(ads) → O(ads) + CO2(gas); RER2 is COgas + O2(ads) → CO3(ads) → O(ads) + CO2(gas); RLH1 refers to CO(ads) + O2(ads) → O(ads) + CO2(gas); RLH2 refers to CO(ads) + O2(ads) → OOCO(ads) → O(ads) + CO2(gas) and RLH3 refers to O2(ads) + CO(ads)→ O(ads) + O(ads) + CO(ads) → O(ads) + CO2(gas). These pathways have low energy barriers and are strongly exothermic, suggesting the Cu13 cluster is very favorable catalyst for the first CO oxidation. However, there are higher energy barriers of 99. 8 and 45.4 kJ/mol in the process of producing and decomposing intermediates along the RLH2 and RER2, indicating that RER1, RLH1 and RLH3 are superior pathways with lower energy barriers, especially the RER1 channel. Thereafter, the second CO is more prone to react with the remaining oxygen atom on Cu13 along the ER channel in comparison with the LH pathway, in which the moderate barrier is 70.0 kJ/mol and it is exothermic by 59.6 kJ/mol. Furthermore, the interaction between the absorbate and cluster is analyzed by electronic analysis to gain insights into high activity of the copper cluster.展开更多
A series of Au/CuOx-TiO2 with various Cu/Ti ratios were prepared. CuOx/TiO2 was prepared by incipient-wetness im- pregnation with aqueous solution of copper nitrate. Au catalysts were prepared by deposition-precipitat...A series of Au/CuOx-TiO2 with various Cu/Ti ratios were prepared. CuOx/TiO2 was prepared by incipient-wetness im- pregnation with aqueous solution of copper nitrate. Au catalysts were prepared by deposition-precipitation method at pH 7 and 338 K. The catalysts were characterized by inductively-coupled plasma-mass spectrometry, temperature pro- gramming reduction, X-ray diffraction, transmission electron microscopy, high-resolution transmission electron mi- croscopy and X-ray photoelectron spectroscopy. The reaction was carried out in a fixed bed reactor with a feed con- taining 1% CO in air at WHSV of 120,000 mL/h·g. High gold dispersion and narrow size distribution was obtained. The addition of CuOx in Au/TiO2 enhanced the activity on CO oxidation significantly. CuOx was in amorphous state which could stabilize the Au nanoparticles. Cu was in Cu1+ state. Cu donated partial electrons to Au. The interactions among Au, Cu1+ and TiO2 account for the high catalytic activity for CO oxidation. The significant promotional effect of CuOx on CO oxidation at low temperature was demonstrated.展开更多
基金the financial support from National Natural Science Foundation of China (No. 21972102)National Key Research and Development Program of China (2021YFA0910400)+3 种基金Natural Science Foundation of Jiangsu Province (BK20200991)Suzhou Science and Technology Planning Project (SS202016)the USTS starting fund (No.332012104)the Natural Science Foundation of Suzhou University of Science and Technology (No.342134401)。
文摘Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still face relatively low NH3yield rate and poor stability. We present here a core-shell heterostructure comprising cobalt oxide anchored on copper oxide nanowire arrays(CuO NWAs@Co_(3)O_(4)) for efficient NRA. The CuO NWAs@Co_(3)O_(4)demonstrates significantly enhanced NRA performance in alkaline media in comparison with plain CuO NWAs and Co_(3)O_(4)flocs. Especially, at-0.23 V vs. RHE, NH_(3) yield rate of the CuO NWAs@Co_(3)O_(4)reaches 1.915 mmol h^(-1)cm^(-2),much higher than those of CuO NWAs(1.472 mmol h^(-1)cm^(-2)), Co_(3)O_(4)flocs(1.222 mmol h^(-1)cm^(-2)) and recent reported Cu-based catalysts.It is proposed that the synergetic effects of the heterostructure combing atom hydrogen adsorption and nitrate reduction lead to the enhanced NRA performance.
文摘The solid structures and thermostabilities of Cu-Fe-O and Cu-Fe-Ce-O supported on alumina were studied by XRD, ESR, Mossbauer and TPR techniques. The studies indicate that there are Fe2CuO4, CuO and alpha-Fe2O3 phases in Cu-Fe-O with the granula of less than 13 nm. With the catalyst pretreatment temperature rising, the crystallite of Fe2CuO4 in the catalysts grows up and that of CuO disappears gradually. The presence of Ce leads to the increase of Cu2+ concentration, inhibits the crystal growth of CuO and Fe2CuO4 in the catalyst except that of Fe2O3, and eliminates the difference for reductive reaction of oxygen in Fe-O and Cu-O. At 800 degrees C, the crystal growth of Fe2O3 in Cu-Fe-Ce-O is slower than that in Cu-Fe-O, i.e., CeO2 in Cu-Fe-Ce-O inhibits the growth of Fe2O3 phase effectively, and enhances the thermostability of catalysts so as to avoid the sintering of active elements in catalysts. CeO2 promotes the reducibility of catalysts at lower temperature.
文摘Cobalt-Boron oxides containing catalyst CoO·B2O3 (CoB2O4) are synthesized for hydrogen generation by catalytic reforming of basic solution of sodium hypophosphite (NaH2PO2) and identified by chemical and X-ray analysis. Reforming is performed in temperature range of 30°C - 80°C. Reaction rate constants at each value of temperature (k30°C = 8.53 × 10?4 s?1;k40°C = 1.62 × 10?4 s??;k50°C = 3.06 × 10?3 s?1;k60°C = 5.06 × 10?3 s?1;k80°C = 1.39 × 10?2 s?1), temperature coefficient of rate of chemical reaction (γ = 0.917) and activation energy (EA = 49.59 kJ·mol?1) are calculated.
文摘A sulphuric acid bake–leach method for the treatment of mixed copper-cobalt oxide minerals was investigated as an alternative to the reductive leaching method. Sulphuric acid bake-leach process of the mixed copper-cobalt oxide ore was carried out by mixing the sample with sulphuric acid followed by baking of the mixture in a muffle furnace. Baking tests were conducted at different conditions such as temperature, time, and varying amounts of acid. The reacted samples were then subjected to water leaching at room temperature to determine the leachability of copper and cobalt from the baked material. The dissolutions of copper and cobalt were dependent on acid concentration with cobalt showing more sensitivity to the amount of acid. Both copper and cobalt were extracted from the baked material within short leaching times and without the addition of reducing agents. The outcome of this work has shown that the sulphuric acid bake-leach process is a possible alternative to the reductive leaching method for copper-cobalt oxide ores.
文摘A microreactor system was used to study the catalytic reaction of NO+CO→1/2 N_2+CO_2 over Cu,Fe, Mn,Cr,and Ce oxides supported on alumina,and the effect of adding Ce in supported Cu-M-O(M=Mn,Fe and Cr) catalysts on their catalytic activities for the topic reaction and the concentration of N_2O produced.It was found that the catalytic activity order of the single-element oxide is:CuO>Fe_2O_3≈Cr_2O_3> MnO_2>CeO_2>NiO.Cu-Mn-O is more active than CuO,and Cu-Fe-O is more active than Cu-Mn-O and Cu-Cr-O for NO+CO reaction.This study shows that the addition of Ce in supported Cu-M-O can promote their catalytic activities Jot the topic reaction,which makes the reaction of 2NO+CO→N_2O+CO_2 fast,and N_2O is an intermediate compound produced during NO+CO reaction.
文摘A series of alumina supported cobalt oxide based catalysts doped with noble metals such as ruthenium and platinum were prepared by wet impregnation method.The variables studied were difference ratio and calcination temperatures.Pt/Co(10∶90)/Al2O3 catalyst calcined at 700 ℃ was found to be the best catalyst which able to convert 70.10% of CO2 into methane with 47% of CH4 formation at maximum temperature studied of 400 ℃.X-ray diffraction analysis showed that this catalyst possessed the active site Co3O4 in face-centered cubic and PtO2 in the orthorhombic phase with Al2O3 existed in the cubic phase.According to the FESEM micrographs,both fresh and spent Pt/Co(10∶90)/Al2O3 catalysts displayed small particle size with undefined shape.Nitrogen Adsorption analysis showed that 5.50% reduction of the total surface area for the spent Pt/Co(10∶90)/Al2O3 catalyst.Meanwhile,Energy Dispersive X-ray analysis(EDX) indicated that Co and Pt were reduced by 0.74% and 0.14% respectively on the spent Pt/Co(10∶90)/Al2O3catalyst.Characterization using FT-IR and TGA-DTA analysis revealed the existence of residual nitrate and hydroxyl compounds on the Pt/Co(10∶90)/Al2O3 catalyst.
文摘Supported Cu catalysts for low-temperature CO oxidation were prepared by solvated metal atom impregnation (SMAI). X-ray photoelectron spectroscopy (XPS) investigations indicated that the copper in all the samples was in a metallic state. XRD measurements showed that the mean diameters of Cu particles prepared by SMAI were small. Catalytical tests showed that the SMAI catalyst had high CO oxidation activity.
基金Funded by the Guiding Research Project of Hubei Province Department of Education(No.B2016098)
文摘Metal-organic framework(MOF) material MIL-53(A1) with high thermal stability was prepared by a solvothermal method,serving as a support material of cerium doped copper catalyst(Ce-Cu)/MIL-53(A1) material for CO oxidation with high catalytic activity.The catalytic performance between the(CuCe)/MIL-53(A1) and the Cu/MIL-53(A1) catalytic material was compared to understand the catalytic behavior of the catalysts.The catalysts were characterized by thermogravimetric-differential scanning calorimetry(TGDSC),N2 adsorption- desorption,X-ray diffraction(XRD),and transmission electron microscopy(TEM).The characterization results showed that MIL-53(A1) had good stability and high surface areas,the(Ce-Cu)nanoparticles on the MIL-53(A1) support was uniform.Therefore,the heterogeneous catalytic composite materials(Ce-Cu)/MIL-53(A1) catalyst exhibited much higher activity than that of the Cu/MIL- 53(A1) catalyst in CO oxidation test,with 100%conversion at 80 ℃.The results reveal that(Cu-Ce)/MIL-53(A1) is the suitable candidate for achieving low temperature and higher activity CO oxidation catalyst of MOFs.
文摘Several researches have been reported about the characteristic of β-Ga_2O_3 nanowires which was synthesized on nickel oxide particle.But indeed,recent researches about synthesis of β-Ga_2O_3 nanowires on oxide-assisted transition metal are limited to nickel or cobalt oxide catalyst.In this work,Gallium oxide(β-Ga_2O_3)nanowires were synthesized by a simple thermal evaporation method from gallium powder in the range of 700-1000℃ using the iron,nickel,copper,cobalt and zinc oxide as a catalyst,respectively.The β-Ga_2O_3 nanowires with single crystalline without defects were successfully synthesized at the reaction temperature of 850,900 and 950℃ in all the catalysts.But optimum experimental condition in synthesis of nanowires varied with the kind of catalyst.As increasing synthesis temperature,the morphology of gallium oxide nanowires changed from nanowires to nanorods,and its diameter increased.From these results,we could be proposed that the growth mechanism of β-Ga_2O_3 nanowires was changed with synthesis temperature of nanowires.Microstructure and morphology of Synthesized nanowire was characterized by HR-TEM,FE-SEM,EDX and XRD.
文摘Four perovskite-type complex oxides (LaNiO_3, La_2NiO_4, LaCoO_3 andLa_2CoO_4) were successfully prepared using two sol-gel methods, the Pechini method (PC) and thecitric acid complexing method (CC). The catalysts were characterized by XRD and TPR. Afterreduction, the activity of the catalysts in the CO_2 reforming of methane was tested. Ni-basedcatalysts from La_2NiO_4 precursors were the most active and stable catalyst after calcination above850 ℃, which gave a methane conversion of 0.025 mmol/(g·s) for those prepared by the PC methodand 0.020 mmol/(g·s) by the CC method. It was proposed that the well-defined structure and lowerreducibility is responsible for the unusual catalytic behavior observed over the pre-reducedLa2NiO_4 catalyst.
基金supported by the National Natural Science Foundation of China(Nos.51574090 and 21773030)Natural Science Foundation of Fujian Province(2017J01409)
文摘We have studied the reaction mechanism of CO oxidation on the Cu13 cluster via density functional theory. There are two main reaction pathways to be considered: Eley-Rideal(ER) and Langmuir-Hinshelwood(LH) mechanisms, respectively. According to these two main reaction mechanisms, we have obtained five reaction pathways for the first CO oxidation(denoted as RER1,RER2, RLH1, RLH2 and RLH3, respectively): RER1 is COgas + O2(ads) → O(ads) + CO2(gas); RER2 is COgas + O2(ads) → CO3(ads) → O(ads) + CO2(gas); RLH1 refers to CO(ads) + O2(ads) → O(ads) + CO2(gas); RLH2 refers to CO(ads) + O2(ads) → OOCO(ads) → O(ads) + CO2(gas) and RLH3 refers to O2(ads) + CO(ads)→ O(ads) + O(ads) + CO(ads) → O(ads) + CO2(gas). These pathways have low energy barriers and are strongly exothermic, suggesting the Cu13 cluster is very favorable catalyst for the first CO oxidation. However, there are higher energy barriers of 99. 8 and 45.4 kJ/mol in the process of producing and decomposing intermediates along the RLH2 and RER2, indicating that RER1, RLH1 and RLH3 are superior pathways with lower energy barriers, especially the RER1 channel. Thereafter, the second CO is more prone to react with the remaining oxygen atom on Cu13 along the ER channel in comparison with the LH pathway, in which the moderate barrier is 70.0 kJ/mol and it is exothermic by 59.6 kJ/mol. Furthermore, the interaction between the absorbate and cluster is analyzed by electronic analysis to gain insights into high activity of the copper cluster.
文摘A series of Au/CuOx-TiO2 with various Cu/Ti ratios were prepared. CuOx/TiO2 was prepared by incipient-wetness im- pregnation with aqueous solution of copper nitrate. Au catalysts were prepared by deposition-precipitation method at pH 7 and 338 K. The catalysts were characterized by inductively-coupled plasma-mass spectrometry, temperature pro- gramming reduction, X-ray diffraction, transmission electron microscopy, high-resolution transmission electron mi- croscopy and X-ray photoelectron spectroscopy. The reaction was carried out in a fixed bed reactor with a feed con- taining 1% CO in air at WHSV of 120,000 mL/h·g. High gold dispersion and narrow size distribution was obtained. The addition of CuOx in Au/TiO2 enhanced the activity on CO oxidation significantly. CuOx was in amorphous state which could stabilize the Au nanoparticles. Cu was in Cu1+ state. Cu donated partial electrons to Au. The interactions among Au, Cu1+ and TiO2 account for the high catalytic activity for CO oxidation. The significant promotional effect of CuOx on CO oxidation at low temperature was demonstrated.