The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of...The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.展开更多
Developing a suitable catalyst for the elimination of highly toxic carbonyl sulfide(COS)and hydrogen sulfide(H_(2)S) is of great significance in terms of industrial safety and environmental protection.We demonstrate h...Developing a suitable catalyst for the elimination of highly toxic carbonyl sulfide(COS)and hydrogen sulfide(H_(2)S) is of great significance in terms of industrial safety and environmental protection.We demonstrate here the facile synthesis of graphitized 2D micro-meso-macroporous carbons by one-step carbonization of a mixture of urea and glucose at 700–900℃.The as-synthesized graphitized catalysts,designated as 2DNHPC-x(x=urea/glucose mass ratio),are endowed with an ultra-high concentration(12.9–20.2 wt%)of stable and versatile nitrogen sites(e.g.pyrrole and pyridine)which are anchored on the surface via stable covalent bonding.As a result,the 2D-NHPC-x are active in catalytic hydrolysis of COS on pyrrolic N to H_(2)S,and the H_(2)S can be subsequently captured on pyridinic N and converted to elemental sulfur at ambient conditions over the same materials.Among the prepared catalysts,2D-NHPC-x can catalytically hydrolysize 91%of COS to H_(2)S at 30℃,whereas the conversion ratio over the common catalysts g-C_(3)N_(4)and Fe_(2)O_(3)are below 6.0%.Furthermore,these catalysts also exhibit H_(2)S conversion and sulfur selectivity of nearly 100%at 180℃with long-time durability,which is higher than those of the most reported carbonbased catalysts.In contrast,the H_(2)S capacities of activated carbon,ordered mesoporous carbons(OMC)and N-doped OMC are 3.9,1.5 and2.39 mmol g^(-1),respectively.Both the experimental and theoretical results are disclosed that 2D-NHPC-x are superior to the nitrogen-doped porous materials ever applied in simultaneous catalytic elimination of both COS and H_(2)S.展开更多
Developing catalysts with not only hydrogenation activity but also cracking activity is very important for the advancement of suspended-bed hydrocracking technology.Within this respect,MoS_(2)/SiO_(2)-Al_(2)O_(3)bifun...Developing catalysts with not only hydrogenation activity but also cracking activity is very important for the advancement of suspended-bed hydrocracking technology.Within this respect,MoS_(2)/SiO_(2)-Al_(2)O_(3)bifunctional catalyst is a kind of typical catalysts with both hydrogenation and cracking activity.Herein,a series of Zr-doped SiO_(2)-Al_(2)O_(3)mixed oxides were synthesized by a sol-gel coupled with hydrothermal method.The synthesized mixed oxides were characterized for chemical structures and acidic properties.It is found that doping SiO_(2)-Al_(2)O_(3)with Zr atoms significantly increases the numbers of acidic sites.The Zr-doped SiO_(2)-Al_(2)O_(3)mixed oxides were then combined with dispersed MoS_(2),which was in-situ produced from oil-soluble Mo precursors,to fabricate a novel kind of bifunctional catalysts for suspended-bed hydrocracking of heavy oils.Owing to the significantly increased numbers of acidic sites in Zr-doped SiO_(2)-Al_(2)O_(3)mixed oxides,corresponding bifunctional catalysts demonstrate much enhanced activity for suspended-bed hydrocracking of heavy oils in relative to MoS_(2)/SiO_(2)-Al_(2)O_(3)bifunctional catalysts.展开更多
In this study, the effects of copper(Cu) additive on the catalytic performance of Ag/SBA-15 in complete soot combustion were investigated. The soot combustion performance of bimetallic Ag–Cu/SBA-15 catalysts was high...In this study, the effects of copper(Cu) additive on the catalytic performance of Ag/SBA-15 in complete soot combustion were investigated. The soot combustion performance of bimetallic Ag–Cu/SBA-15 catalysts was higher than that of monometallic Ag and Cu catalysts. The optimum catalytic performance was acquired with the 5 Ag_1-Cu_(0.1)/SBA-15 catalyst, on which the soot combustion starts at T_(ig)= 225°C with a T_(50)= 285°C. The temperature for 50% of soot combustion was lower than that of conventional Ag-based catalysts to more than 50°C(Aneggi et al., 2009). Physicochemical characterizations of the catalysts indicated that addition of Cu into Ag could form smaller bimetallic Ag–Cu nanolloy particles, downsizing the mean particle size from 3.7 nm in monometallic catalyst to 2.6 nm in bimetallic Ag–Cu catalyst. Further experiments revealed that Ag and Cu species elicited synergistic effects, subsequently increasing the content of surface active oxygen species. As a result, the structure modifications of Ag by the addition of Cu strongly intensified the catalytic performance.展开更多
Being abundant and active,Fe_(2)O_(3) is suitable for selective oxidation of H_(2)S.However,its practical application is limited due to the poor sulfur selectivity and rapid deactivation.Herein,we report a facile temp...Being abundant and active,Fe_(2)O_(3) is suitable for selective oxidation of H_(2)S.However,its practical application is limited due to the poor sulfur selectivity and rapid deactivation.Herein,we report a facile template-free hydrothermal method to fabricate porousα-Fe_(2)O_(3)/SnO_(2) composites with hierarchical nanoflower that can obviously improve the catalytic performance of Fe_(2)O_(3).It was disclosed that the synergistic effect betweenα-Fe_(2)O_(3) and SnO_(2) promotes the physico-chemical properties ofα-Fe_(2)O_(3)/SnO_(2) composites.Specifically,the electron transfer between the Fe^(2+)/Fe^(3+)and Sn^(2+)/Sn^(4+)redox couples enhances the reducibility ofα-Fe_(2)O_(3)/SnO_(2) composites.The number of oxygen vacancies is improved when the Fe cations incorporate into SnO_(2) structure,which facilitates the adsorption and activation of oxygen species.Additionally,the porous structure improves the accessibility of H_(2) S to active sites.Among the composites,Fe1 Sn1 exhibits complete H_(2) S conversion with 100%sulfur selectivity at 220℃,better than those of pureα-Fe_(2)O_(3) and SnO2.Moreover,Fe1 Sn1 catalyst shows high stability and water resistance.展开更多
基金the National Natural Science Foundation of China (92034301,22078063 and 22022804)Major Program of Qingyuan Innovation Laboratory (00121003)the Natural Science Foundation of Fujian Province (2020H6007)。
文摘The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.
基金supported by the National Natural Science Foundation of China (21603034,21576051)the National High Technology Research and Development Program of China (863 Program,2015AA03A402)~~
基金supported by the National Natural Science Foundation of China(22022804,21978052)the Natural Science Foundation for the Distinguished Young Scholar of Fujian Province(2020J06037)the National Key Research and Development Program of China(2018YFA0209304)。
文摘Developing a suitable catalyst for the elimination of highly toxic carbonyl sulfide(COS)and hydrogen sulfide(H_(2)S) is of great significance in terms of industrial safety and environmental protection.We demonstrate here the facile synthesis of graphitized 2D micro-meso-macroporous carbons by one-step carbonization of a mixture of urea and glucose at 700–900℃.The as-synthesized graphitized catalysts,designated as 2DNHPC-x(x=urea/glucose mass ratio),are endowed with an ultra-high concentration(12.9–20.2 wt%)of stable and versatile nitrogen sites(e.g.pyrrole and pyridine)which are anchored on the surface via stable covalent bonding.As a result,the 2D-NHPC-x are active in catalytic hydrolysis of COS on pyrrolic N to H_(2)S,and the H_(2)S can be subsequently captured on pyridinic N and converted to elemental sulfur at ambient conditions over the same materials.Among the prepared catalysts,2D-NHPC-x can catalytically hydrolysize 91%of COS to H_(2)S at 30℃,whereas the conversion ratio over the common catalysts g-C_(3)N_(4)and Fe_(2)O_(3)are below 6.0%.Furthermore,these catalysts also exhibit H_(2)S conversion and sulfur selectivity of nearly 100%at 180℃with long-time durability,which is higher than those of the most reported carbonbased catalysts.In contrast,the H_(2)S capacities of activated carbon,ordered mesoporous carbons(OMC)and N-doped OMC are 3.9,1.5 and2.39 mmol g^(-1),respectively.Both the experimental and theoretical results are disclosed that 2D-NHPC-x are superior to the nitrogen-doped porous materials ever applied in simultaneous catalytic elimination of both COS and H_(2)S.
基金the National Key Research&Development Program of China(2018YFA0209403)the National Natural Science Foundation of China(U1662108)the Science and Technology Project of Fujian Province(FG-2016002).
文摘Developing catalysts with not only hydrogenation activity but also cracking activity is very important for the advancement of suspended-bed hydrocracking technology.Within this respect,MoS_(2)/SiO_(2)-Al_(2)O_(3)bifunctional catalyst is a kind of typical catalysts with both hydrogenation and cracking activity.Herein,a series of Zr-doped SiO_(2)-Al_(2)O_(3)mixed oxides were synthesized by a sol-gel coupled with hydrothermal method.The synthesized mixed oxides were characterized for chemical structures and acidic properties.It is found that doping SiO_(2)-Al_(2)O_(3)with Zr atoms significantly increases the numbers of acidic sites.The Zr-doped SiO_(2)-Al_(2)O_(3)mixed oxides were then combined with dispersed MoS_(2),which was in-situ produced from oil-soluble Mo precursors,to fabricate a novel kind of bifunctional catalysts for suspended-bed hydrocracking of heavy oils.Owing to the significantly increased numbers of acidic sites in Zr-doped SiO_(2)-Al_(2)O_(3)mixed oxides,corresponding bifunctional catalysts demonstrate much enhanced activity for suspended-bed hydrocracking of heavy oils in relative to MoS_(2)/SiO_(2)-Al_(2)O_(3)bifunctional catalysts.
基金the National Natural Science Foundation of China(Nos.21403178,21473145,21503173,and 91545115)the National High-tech R&D Program(2015AA03A402)the Program for Innovative Research Team in Chinese Universities(No.IRT_14R31)
文摘In this study, the effects of copper(Cu) additive on the catalytic performance of Ag/SBA-15 in complete soot combustion were investigated. The soot combustion performance of bimetallic Ag–Cu/SBA-15 catalysts was higher than that of monometallic Ag and Cu catalysts. The optimum catalytic performance was acquired with the 5 Ag_1-Cu_(0.1)/SBA-15 catalyst, on which the soot combustion starts at T_(ig)= 225°C with a T_(50)= 285°C. The temperature for 50% of soot combustion was lower than that of conventional Ag-based catalysts to more than 50°C(Aneggi et al., 2009). Physicochemical characterizations of the catalysts indicated that addition of Cu into Ag could form smaller bimetallic Ag–Cu nanolloy particles, downsizing the mean particle size from 3.7 nm in monometallic catalyst to 2.6 nm in bimetallic Ag–Cu catalyst. Further experiments revealed that Ag and Cu species elicited synergistic effects, subsequently increasing the content of surface active oxygen species. As a result, the structure modifications of Ag by the addition of Cu strongly intensified the catalytic performance.
基金supported by the National Natural Science Fund for Distinguished Young Scholars of China(No.21825801)National Natural Science Foundation of China(Nos.21677036,21878052 and 21773030)。
文摘Being abundant and active,Fe_(2)O_(3) is suitable for selective oxidation of H_(2)S.However,its practical application is limited due to the poor sulfur selectivity and rapid deactivation.Herein,we report a facile template-free hydrothermal method to fabricate porousα-Fe_(2)O_(3)/SnO_(2) composites with hierarchical nanoflower that can obviously improve the catalytic performance of Fe_(2)O_(3).It was disclosed that the synergistic effect betweenα-Fe_(2)O_(3) and SnO_(2) promotes the physico-chemical properties ofα-Fe_(2)O_(3)/SnO_(2) composites.Specifically,the electron transfer between the Fe^(2+)/Fe^(3+)and Sn^(2+)/Sn^(4+)redox couples enhances the reducibility ofα-Fe_(2)O_(3)/SnO_(2) composites.The number of oxygen vacancies is improved when the Fe cations incorporate into SnO_(2) structure,which facilitates the adsorption and activation of oxygen species.Additionally,the porous structure improves the accessibility of H_(2) S to active sites.Among the composites,Fe1 Sn1 exhibits complete H_(2) S conversion with 100%sulfur selectivity at 220℃,better than those of pureα-Fe_(2)O_(3) and SnO2.Moreover,Fe1 Sn1 catalyst shows high stability and water resistance.
