The catalytic cracking of light diesel oil （235–337 ＆#176;C） over gold‐modified ZSM‐5 was investigated in a small confined fluidized bed at 460 ＆#176;C and ambient pressure. Different Au/ZSM‐5 catalysts were p...The catalytic cracking of light diesel oil （235–337 ＆#176;C） over gold‐modified ZSM‐5 was investigated in a small confined fluidized bed at 460 ＆#176;C and ambient pressure. Different Au/ZSM‐5 catalysts were prepared by a modified deposition‐precipitation method by changing the preparation procedure and the amount of gold loading and were characterized by X‐ray diffraction, N2 adsorp‐tion‐desorption, temperature‐programmed desorption of NH3, transmission electron microscopy and inductively coupled plasma spectrometer. It was found that a small amount of gold had a posi‐tive effect on the catalytic cracking of light diesel oil and increased propylene production at a rela‐tively low temperature. The maintenance of the ZSM‐5 MFI structure, pore size distribution and the density of weak and strong acid sites of the Au/ZSM‐5 catalysts depended on the preparation pa‐rameters and the Au loading. Simultaneous enhancement of the micro‐activity and propylene pro‐duction relies on a synergy between the pore size distribution and the relative intensity of the weak and strong acid sites. A significant improvement in the micro‐activity index with an increase of 4.5 units and in the propylene selectivity with an increase of 23.2 units was obtained over the Au/ZSM‐5 catalyst with an actual Au loading of 0.17 wt%.展开更多
Nation-membrane-based proton exchange fuel cells （PEMFCs） typically operate at below 100 ℃. However, H3PO4-doped polybenzimidazole （PBI）-based PEMFCs can operate at 100-200 ℃. This is advantageous because of acc...Nation-membrane-based proton exchange fuel cells （PEMFCs） typically operate at below 100 ℃. However, H3PO4-doped polybenzimidazole （PBI）-based PEMFCs can operate at 100-200 ℃. This is advantageous because of accelerated reaction rates and enhanced tolerance to poisons such as CO and S02, which can arise from reformed gas or the atmosphere. However, the strong adsorption of phosphoric anions on the Pt surface dramatically decreases the electrocatalytic activity. This study exploits the ＂third-body effect＂, in which a small amount of organic molecules are pre-adsorbed on the Pt surface to inhibit the adsorption of phosphoric anions. Pre-adsorbate species inhibit the ad- sorption of phosphoric anions, but can also partially occlude active sites. Thus, the optimum pre-adsorbate coverage is studied by correlating the oxygen reduction reaction （ORR） activity of Pt with pre-adsorbate coverage on the Pt surface. The influence of the pre-adsorbate molecule length is investigated using the organic amines, butylamine, octylamine, and dodecylamine, in both 0.1 mol/L HCI04 and 0.1 mol/L H3P04. Such amines readily bond to the Pt surface. In aqueous HCI04 electrolyte, the ORR activity of Pt decreases monotonically with increasing pre-adsorbate coverage. In aqueous H3P04 electrolyte, the ORR activity of Pt initially increases and then decreases with in- creasing pre-adsorbate coverage. The maximum ORR activity in H3P04 occurs at a pre-adsorbate coverage of around 20%. The effect of molecular length of the pre-adsorbate is negligible, but its coverage strongly affects the degree to which phosphoric anion adsorption is inhibited. Butylamine adsorbs to Pt at partial active sites, which decreases the electrochemically active surface area. Ad- sorbed butylamine may also modify the electronic structure of the Pt surface. The ORR activity in the phosphoric acid electrolyte remains relatively low, even when using the pre-adsorbate modified Pt/C catalysts. Further development of the catalyst and electrolyte is required before the commercialization of H3PO4-PBl-based PEMFCs can be realized.展开更多
Alkaline water splitting is a promising technology for“green hydrogen”generation.To improve its efficiency,highly robust catalysts are required to reduce the overpotential for low electrical power consumption.Hetero...Alkaline water splitting is a promising technology for“green hydrogen”generation.To improve its efficiency,highly robust catalysts are required to reduce the overpotential for low electrical power consumption.Heteroatom modification is one of the most effective strategies for boosting catalytic performance,as it can regulate the physicochemical properties of host catalysts to improve their intrinsic activity.Herein,aiming to provide an overview of the impact of heteroatoms on catalytic activity at the atomic level,we present a review of the key role of heteroatoms in enhancing reaction kinetics based on the reaction pathways of the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in alkaline media.In particular,the introduction of heteroatoms can directly and indirectly optimize the interactions between the active sites and intermediates,thus improving the intrinsic activity.To clearly illustrate this influence in detail,we have summarized a series of representative heteroatom-modified electrocatalysts and discussed the important roles of heteroatoms in the OER and HER reaction pathways.Finally,some challenges and perspectives for heteroatom-modified electrodes are discussed.We hope that this review will be helpful for the development of efficient and low-cost electrocatalysts for water electrolysis and other energy conversion applications.展开更多
Controllably mounting foreign atoms on the surfaces of earth-abundant electrocatalysts strongly improve their surface electronic properties for optimizing the catalytic performance of surficial sites to an unusual lev...Controllably mounting foreign atoms on the surfaces of earth-abundant electrocatalysts strongly improve their surface electronic properties for optimizing the catalytic performance of surficial sites to an unusual level,and provides a good platform to gain deep insights into catalytic reactions.The present work describes,employing ultrafine W2C nanoislands(average size:2.3 nm)monodispersed on the N,P dual-doped carbon frameworks as a model system,how to regulate the atomic phosphorous-mounting effect on the surfaces of W_(2)C to derive an active and stable P-mounting W_(2)C(WCP)catalyst for both acidic and alkaline hydrogen evolution reaction(HER).Since in situ phosphorus substitution into carbon sites of preformed W_(2)C nanoislands gradually proceeds from surfaces to solids,so that using a proper amount of phosphorus sources can readily control the surface mounting level to avoid the mass P-doping into the bulk.By this way,the activity per active site of WCP catalyst with robust stability can be optimized to 0.07 and 0.56 H_(2 )s^(-1) at-200 mV overpotential in acid and base,respectively,which reach up to the several-fold of pure-phase W_(2)C(0.01 and 0.05 H_(2) s^(-1)).Theoretical investigations suggest that compared with solid P doping,the P mounting on W_(2)C surface can more remarkably enhance its metallicity and decrease the hydrogen release barrier.This finding disclosed a key correlation between surface foreign atom-mounting and catalytic activity,and suggested a logical extension to other earth-abundant catalysts for various catalytic reactions.展开更多
A new approach modification reactions Atherton-Todd, Betty, Mannich and Doebner reactions with of arsine, stibine and bismuthine have been proposed in organometallic chemistry of these elements. These new reactions ca...A new approach modification reactions Atherton-Todd, Betty, Mannich and Doebner reactions with of arsine, stibine and bismuthine have been proposed in organometallic chemistry of these elements. These new reactions can be used for the synthesis of drugs and biologically active organic compound of arsenic, antimony and bismuth. A possible new mechanism of the reaction is proposed.展开更多
A Pr-doped TiO2-NTs/SnO2-Sb electrode was prepared by a simple method, cyclic voltarnmetry （CV）. The methyl orange （MO）aqueous solution was selected as a simulated wastewater. The ordered microstructural TiO2-NTs ...A Pr-doped TiO2-NTs/SnO2-Sb electrode was prepared by a simple method, cyclic voltarnmetry （CV）. The methyl orange （MO）aqueous solution was selected as a simulated wastewater. The ordered microstructural TiO2-NTs substrate was synthesized by an electrochemical method to obtain large specific surface area and high space utilization. The phase structure, electrode surface morphology and electrochemical properties of electrodes were characterized by XRD, SEM and electrochemical technology, respectively. The results showed that praseo- dymium oxide was successfully doped into the SnOz-Sb film by CV method. Due to the doped Pr, the oxygen evo- lution potential increased from 2.25 V to 2.40 V. The degradation of MO was investigated by UV-vis. The Ct/C0（φ） was studied as a function to obtain the optimal parameters, such as the amount of doped Pr, current density and initial dye concentration. In addition, the degradation process followed pseudo-first-order reaction kinetics and the rate constant was 0.099 3 min-1. The result indicated that the introduction of Pr reduced the formation of oxygen vacancies or enhanced the formation of adsorbed hydroxyl radical groups on the surface, thus leading to better activity and stability.展开更多
Copper nanoparticles was prepared by ascorbic acid reducing CuC12 solution modified with [ BMIm ] BF4 ionic liquid. The size of copper nanoparticles was obviously affected by the concentration of Cu2＋ . The diameter ...Copper nanoparticles was prepared by ascorbic acid reducing CuC12 solution modified with [ BMIm ] BF4 ionic liquid. The size of copper nanoparticles was obviously affected by the concentration of Cu2＋ . The diameter of nanoparticles was smaller than 10 nm when the Cu2＋ concentration was smaller than 2× 10.2 moL/L. The pH and temperature of reductive reaction had no obvious effect on the size of copper nanoparticles.展开更多
基金supported by the Shandong Taishan Scholarship, the Yantai double-hundreds talents planthe Shandong Natural Science Founda-tion (ZR2015BM006)~~
文摘The catalytic cracking of light diesel oil （235–337 ＆#176;C） over gold‐modified ZSM‐5 was investigated in a small confined fluidized bed at 460 ＆#176;C and ambient pressure. Different Au/ZSM‐5 catalysts were prepared by a modified deposition‐precipitation method by changing the preparation procedure and the amount of gold loading and were characterized by X‐ray diffraction, N2 adsorp‐tion‐desorption, temperature‐programmed desorption of NH3, transmission electron microscopy and inductively coupled plasma spectrometer. It was found that a small amount of gold had a posi‐tive effect on the catalytic cracking of light diesel oil and increased propylene production at a rela‐tively low temperature. The maintenance of the ZSM‐5 MFI structure, pore size distribution and the density of weak and strong acid sites of the Au/ZSM‐5 catalysts depended on the preparation pa‐rameters and the Au loading. Simultaneous enhancement of the micro‐activity and propylene pro‐duction relies on a synergy between the pore size distribution and the relative intensity of the weak and strong acid sites. A significant improvement in the micro‐activity index with an increase of 4.5 units and in the propylene selectivity with an increase of 23.2 units was obtained over the Au/ZSM‐5 catalyst with an actual Au loading of 0.17 wt%.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA09030104)the National Basic Research Program of China(973 Program,2012CB215500)the Key Program of the Chinese Academy of Sciences(KGZD-EW-T08)
文摘Nation-membrane-based proton exchange fuel cells （PEMFCs） typically operate at below 100 ℃. However, H3PO4-doped polybenzimidazole （PBI）-based PEMFCs can operate at 100-200 ℃. This is advantageous because of accelerated reaction rates and enhanced tolerance to poisons such as CO and S02, which can arise from reformed gas or the atmosphere. However, the strong adsorption of phosphoric anions on the Pt surface dramatically decreases the electrocatalytic activity. This study exploits the ＂third-body effect＂, in which a small amount of organic molecules are pre-adsorbed on the Pt surface to inhibit the adsorption of phosphoric anions. Pre-adsorbate species inhibit the ad- sorption of phosphoric anions, but can also partially occlude active sites. Thus, the optimum pre-adsorbate coverage is studied by correlating the oxygen reduction reaction （ORR） activity of Pt with pre-adsorbate coverage on the Pt surface. The influence of the pre-adsorbate molecule length is investigated using the organic amines, butylamine, octylamine, and dodecylamine, in both 0.1 mol/L HCI04 and 0.1 mol/L H3P04. Such amines readily bond to the Pt surface. In aqueous HCI04 electrolyte, the ORR activity of Pt decreases monotonically with increasing pre-adsorbate coverage. In aqueous H3P04 electrolyte, the ORR activity of Pt initially increases and then decreases with in- creasing pre-adsorbate coverage. The maximum ORR activity in H3P04 occurs at a pre-adsorbate coverage of around 20%. The effect of molecular length of the pre-adsorbate is negligible, but its coverage strongly affects the degree to which phosphoric anion adsorption is inhibited. Butylamine adsorbs to Pt at partial active sites, which decreases the electrochemically active surface area. Ad- sorbed butylamine may also modify the electronic structure of the Pt surface. The ORR activity in the phosphoric acid electrolyte remains relatively low, even when using the pre-adsorbate modified Pt/C catalysts. Further development of the catalyst and electrolyte is required before the commercialization of H3PO4-PBl-based PEMFCs can be realized.
文摘Alkaline water splitting is a promising technology for“green hydrogen”generation.To improve its efficiency,highly robust catalysts are required to reduce the overpotential for low electrical power consumption.Heteroatom modification is one of the most effective strategies for boosting catalytic performance,as it can regulate the physicochemical properties of host catalysts to improve their intrinsic activity.Herein,aiming to provide an overview of the impact of heteroatoms on catalytic activity at the atomic level,we present a review of the key role of heteroatoms in enhancing reaction kinetics based on the reaction pathways of the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in alkaline media.In particular,the introduction of heteroatoms can directly and indirectly optimize the interactions between the active sites and intermediates,thus improving the intrinsic activity.To clearly illustrate this influence in detail,we have summarized a series of representative heteroatom-modified electrocatalysts and discussed the important roles of heteroatoms in the OER and HER reaction pathways.Finally,some challenges and perspectives for heteroatom-modified electrodes are discussed.We hope that this review will be helpful for the development of efficient and low-cost electrocatalysts for water electrolysis and other energy conversion applications.
文摘Controllably mounting foreign atoms on the surfaces of earth-abundant electrocatalysts strongly improve their surface electronic properties for optimizing the catalytic performance of surficial sites to an unusual level,and provides a good platform to gain deep insights into catalytic reactions.The present work describes,employing ultrafine W2C nanoislands(average size:2.3 nm)monodispersed on the N,P dual-doped carbon frameworks as a model system,how to regulate the atomic phosphorous-mounting effect on the surfaces of W_(2)C to derive an active and stable P-mounting W_(2)C(WCP)catalyst for both acidic and alkaline hydrogen evolution reaction(HER).Since in situ phosphorus substitution into carbon sites of preformed W_(2)C nanoislands gradually proceeds from surfaces to solids,so that using a proper amount of phosphorus sources can readily control the surface mounting level to avoid the mass P-doping into the bulk.By this way,the activity per active site of WCP catalyst with robust stability can be optimized to 0.07 and 0.56 H_(2 )s^(-1) at-200 mV overpotential in acid and base,respectively,which reach up to the several-fold of pure-phase W_(2)C(0.01 and 0.05 H_(2) s^(-1)).Theoretical investigations suggest that compared with solid P doping,the P mounting on W_(2)C surface can more remarkably enhance its metallicity and decrease the hydrogen release barrier.This finding disclosed a key correlation between surface foreign atom-mounting and catalytic activity,and suggested a logical extension to other earth-abundant catalysts for various catalytic reactions.
文摘A new approach modification reactions Atherton-Todd, Betty, Mannich and Doebner reactions with of arsine, stibine and bismuthine have been proposed in organometallic chemistry of these elements. These new reactions can be used for the synthesis of drugs and biologically active organic compound of arsenic, antimony and bismuth. A possible new mechanism of the reaction is proposed.
基金Supported by the National Natural Science Foundation of China(No.20706041)the Natural Science Foundation of Tianjin(No.09JCYBJC06500)
文摘A Pr-doped TiO2-NTs/SnO2-Sb electrode was prepared by a simple method, cyclic voltarnmetry （CV）. The methyl orange （MO）aqueous solution was selected as a simulated wastewater. The ordered microstructural TiO2-NTs substrate was synthesized by an electrochemical method to obtain large specific surface area and high space utilization. The phase structure, electrode surface morphology and electrochemical properties of electrodes were characterized by XRD, SEM and electrochemical technology, respectively. The results showed that praseo- dymium oxide was successfully doped into the SnOz-Sb film by CV method. Due to the doped Pr, the oxygen evo- lution potential increased from 2.25 V to 2.40 V. The degradation of MO was investigated by UV-vis. The Ct/C0（φ） was studied as a function to obtain the optimal parameters, such as the amount of doped Pr, current density and initial dye concentration. In addition, the degradation process followed pseudo-first-order reaction kinetics and the rate constant was 0.099 3 min-1. The result indicated that the introduction of Pr reduced the formation of oxygen vacancies or enhanced the formation of adsorbed hydroxyl radical groups on the surface, thus leading to better activity and stability.
文摘Copper nanoparticles was prepared by ascorbic acid reducing CuC12 solution modified with [ BMIm ] BF4 ionic liquid. The size of copper nanoparticles was obviously affected by the concentration of Cu2＋ . The diameter of nanoparticles was smaller than 10 nm when the Cu2＋ concentration was smaller than 2× 10.2 moL/L. The pH and temperature of reductive reaction had no obvious effect on the size of copper nanoparticles.
