The conversion of biomass-derived products to fine chemicals and fuels is extremely important for the utilization of renewable energy sources.Water is not only a by-product formed during the hydrogenation of biomass-d...The conversion of biomass-derived products to fine chemicals and fuels is extremely important for the utilization of renewable energy sources.Water is not only a by-product formed during the hydrogenation of biomass-derived oxygenated chemicals,but also an inexpensive and nontoxic solvent.The instability of solid catalysts for aqueous-phase reactions caused by metal leaching and the collapse of a catalyst support represents a significant challenge.In this work,various catalyst stabilization strategies including the nanospace and interfacial confinements that prevent sintering and leaching of metal nanoparticles as well as modification methods for increasing the support stability are summarized and systemically discussed.In addition,feasible approaches to designing stable and efficient heterogeneous catalysts for aqueous-phase reactions are proposed.展开更多
The influence of the dehydration by metal oxides on the synthesis of dimethyl carbonate (DMC) via oxidative carbonylation of methanol was studied. A Cu/Y-zeolite catalyst was prepared by the ion exchange method from...The influence of the dehydration by metal oxides on the synthesis of dimethyl carbonate (DMC) via oxidative carbonylation of methanol was studied. A Cu/Y-zeolite catalyst was prepared by the ion exchange method from CuCl2.2H2O and the commercial NH4-form of the Y type zeolite, The catalyst was characterized by X-ray fluorescence (XRF), N2 adsorption (BET method), X-ray diffraction (XRD), and temperature-programmed de- sorption of ammonia (NH3-TPD) to evaluate its Cu and Cl content, surface area, structure, and acidity. Reaction tests were carried out using an autoclave (batch reactor) for 18 h at 403 K and 5.5 MPa (2CH3OH + 1/2O2 + CO (CH3O)2CO + H2O). The influence of various dehydrating agents (ZnO, MgO, and CaO) was examined with the aim of increasing the methanol conversion (XMeOH, MeOH conversion). The MeOH conversion increased upon addition of metal oxides in the order CaO 〉〉 MgO 〉 ZnO, with the DMC selectivity (SDMC) following the order MgO 〉 CaO 〉 ZnO. The catalysts and dehydrating agents were characterized before and after the oxidative carbonylation of methanol by thermogravimetric and differential thermogravimetric (TG/DTG), and XRD to con- firm that the dehydration reaction occurred via the metal oxide (MO + H2O →M(OH)2). The MeOH conversion increased from 8.7% to 14.6% and DMC selectivity increased from 39.0% to 53.1%, when using the dehydrating azent CaO.展开更多
Hydrogen is a promising sustainable energy to replace fossil fuels owning to its high specific energy and environmental friendliness.Alkaline water electrolysis has been considered as one of the most prospective techn...Hydrogen is a promising sustainable energy to replace fossil fuels owning to its high specific energy and environmental friendliness.Alkaline water electrolysis has been considered as one of the most prospective technologies for large scale hydrogen production.To boost the sluggish kinetics of hydrogen evolution reaction(HER)in alkaline media,abundant materials have been designed and fabricated.Herein,we summarize the key achievements in the development of layered transition-metal hydroxides[TM(OH)x]for efficient alkaline HER.Based on the structure of TM(OH)x,the mechanism of synergistic effect between TM(OH)x and HER active materials is illuminated firstly.Then,recent progress of TM(OH)x-based HER catalysts to optimize the synergistic effect are categorized as TM(OH)x and active materials,including species,structure,morphology and interaction relationship.Furthermore,TM(OH)x-based overall water splitting electrocatalysts and electrodes are summarized in the design principles for high activity and stability.Finally,some of key challenges for further developments and applications of hydrogen production are proposed.展开更多
Promoted by active indium produced in situ by Sm/InCl3 ?4H2O system, arylidenecyano- acetates undergo reductive cyclodimerization to afford cyclopentamine derivatives with high stereoselectivity under mild conditions ...Promoted by active indium produced in situ by Sm/InCl3 ?4H2O system, arylidenecyano- acetates undergo reductive cyclodimerization to afford cyclopentamine derivatives with high stereoselectivity under mild conditions in aqueous media.展开更多
In reverse water gas shift (RWGS) reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were...In reverse water gas shift (RWGS) reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, inductively coupled plasma atomic emission spectrometer (ICP-AES), temperature programmed reduction (H2-TPR), CO chemisorption, energy dispersive X-ray (EDX) and scanning electron microscopy (SEM) techniques. Kinetic properties of all catalysts were investigated in a batch re- actor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/AlzO3 catalyst enhances its activity as compared to Fe/AlaO3. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/AlzO3 catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fez(MoO4)3 phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fez(MoO4)3 phase has low reducibility, therefore the Fe2(MoO4)3 phase significantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al2O3 catalyst. Overall, this study introduces Fe-Mo/Al2O3 as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.展开更多
The feasibility of rhenium (Re) production by irradiating tungsten (W) metal in a medium size fast reactor was evaluated by using a Monte Carlo code. The fast reactor can produce about 50 kilograms of Re per every...The feasibility of rhenium (Re) production by irradiating tungsten (W) metal in a medium size fast reactor was evaluated by using a Monte Carlo code. The fast reactor can produce about 50 kilograms of Re per every 3 years, which corresponds 10% of Japanese domestic production. The specific activity of Re can be reduced below the exemption level or even the natural Re level if W and osmium is separated after the irradiation. The use of ZrD1.7 moderator reduces the specific activity by half compared to that of ZrH1.7 case, and even the no moderator case is permissible to produce the production of Re which has lower specific reactivity than that of natural Re.展开更多
The performance of the two newly developed bimetallic catalysts based on the precursor, Mo/Al_2O_3, was compared for reverse water gas shift(RWGS) reaction. The structures of the precursor and the catalysts were studi...The performance of the two newly developed bimetallic catalysts based on the precursor, Mo/Al_2O_3, was compared for reverse water gas shift(RWGS) reaction. The structures of the precursor and the catalysts were studied using X-ray diffraction(XRD), Brunauer–Emmett–Teller(BET) analysis, inductively coupled plasma-atomic emission spectrometry(ICP-AES), CO chemisorption, temperature programmed reduction of hydrogen(H_2-TPR) and scanning electron microscopy(SEM) techniques. The activity of Fe-Mo and Co-Mo catalysts was compared in a fixed bed reactor at different temperatures. It is shown that the Co-Mo catalyst has higher CO_2 conversion at all temperature level. The time-on-stream(TOS) analysis of the activity of catalysts for the RWGS reaction was carried out over a continuous period of 60h for both catalysts. The Fe-Mo/Al_2O_3 catalyst exhibits good stability within a period of 60h, however, the Co-Mo/Al_2O_3 is gradually deactivated after 50h of reaction time. Existence of(Fe_2(MoO4_))_3 phase in Fe-Mo/Al_2O_3 catalyst makes this catalyst more stable for RWGS reaction.展开更多
Hexamethylenediamine(HMDA) is an important reagent for the synthesis of Nylon-6,6, and it is usually produced by the hydrogenation of adiponitrile using a toxic reagent of hydrocyanic acid. Herein, we developed an env...Hexamethylenediamine(HMDA) is an important reagent for the synthesis of Nylon-6,6, and it is usually produced by the hydrogenation of adiponitrile using a toxic reagent of hydrocyanic acid. Herein, we developed an environmental friendly route to produce HMDA via catalytic reductive amination of 1,6-hexanediol(HDO) in the presence of hydrogen. The activities of several heterogeneous metal catalysts such as supported Ni, Co, Ru, Pt, Pd catalysts were screened for the present reaction in supercritical ammonia without any additives. Among the catalysts examined, Ru/Al_2O_3 presented a high catalytic activity and highest selectivity for the desired product of HMDA. The high performance of Ru/Al_2O_3 was discussed based on the Ru dispersion and the surface properties like the acid-basicity. In addition, the reaction parameters such as reaction temperature,time, H_2 and NH_3 pressure were examined, and the reaction processes were discussed in detail.展开更多
Carbon dots (CDs) with average diameter of 3.1 ± 0.5 nm were facilely synthesized with candle soot through hydrothermal reaction in sodium hydroxide aqueous solution. The as-prepared CDs were covered with a lot o...Carbon dots (CDs) with average diameter of 3.1 ± 0.5 nm were facilely synthesized with candle soot through hydrothermal reaction in sodium hydroxide aqueous solution. The as-prepared CDs were covered with a lot of hydroxyls, possessed properties of good water-solubility, anti-photobleaching, salt tolerance, and low cytotoxicity, and had a fluorescence quantum yield (QY) of about 5.5%. The fluorescence of the hydroxyls-coated CDs could be selectively quenched by metal ions such as Cr3+, Al3+ and Fe3+, which is because these metals can easily combine with the hydroxyl groups on the surface of CDs and induce aggregation of hydroxyls-coated CDs. Experiments showed that the quenching of Cr3+ had a Sterm-Volmer constant of 1.03 × 107 M-1 with a liner range of 1.0-25.0 μM and detection limit of 60 nM (3σ).展开更多
Development of highly active electrocatalysts for oxygen evolution reaction(OER)is one of the critical issues for water splitting,and most reported catalysts operate at overpotentials above 190 mV.Here we present a mu...Development of highly active electrocatalysts for oxygen evolution reaction(OER)is one of the critical issues for water splitting,and most reported catalysts operate at overpotentials above 190 mV.Here we present a multiphase nickel iron sulfide(MPS)hybrid electrode with a hierarchical structure of iron doped NiS and Ni3S2,possessing a benchmark OER activity in alkaline media with a potential as low as 1.33 V(vs.reversible hydrogen electrode)to drive an OER current density of 10 mA cm^-2.The Fe doped NiS,combined with highly conductive disulfide phase on porous Ni foam,is believed to be responsible for the ultrahigh activity.Furthermore,density functional theory simulation reveals that partially oxidized sulfur sites in Fe doped NiS could dramatically lower the energy barrier for the rate-determining elementary reaction,thus contributing to the active oxygen evolution.展开更多
文摘The conversion of biomass-derived products to fine chemicals and fuels is extremely important for the utilization of renewable energy sources.Water is not only a by-product formed during the hydrogenation of biomass-derived oxygenated chemicals,but also an inexpensive and nontoxic solvent.The instability of solid catalysts for aqueous-phase reactions caused by metal leaching and the collapse of a catalyst support represents a significant challenge.In this work,various catalyst stabilization strategies including the nanospace and interfacial confinements that prevent sintering and leaching of metal nanoparticles as well as modification methods for increasing the support stability are summarized and systemically discussed.In addition,feasible approaches to designing stable and efficient heterogeneous catalysts for aqueous-phase reactions are proposed.
文摘The influence of the dehydration by metal oxides on the synthesis of dimethyl carbonate (DMC) via oxidative carbonylation of methanol was studied. A Cu/Y-zeolite catalyst was prepared by the ion exchange method from CuCl2.2H2O and the commercial NH4-form of the Y type zeolite, The catalyst was characterized by X-ray fluorescence (XRF), N2 adsorption (BET method), X-ray diffraction (XRD), and temperature-programmed de- sorption of ammonia (NH3-TPD) to evaluate its Cu and Cl content, surface area, structure, and acidity. Reaction tests were carried out using an autoclave (batch reactor) for 18 h at 403 K and 5.5 MPa (2CH3OH + 1/2O2 + CO (CH3O)2CO + H2O). The influence of various dehydrating agents (ZnO, MgO, and CaO) was examined with the aim of increasing the methanol conversion (XMeOH, MeOH conversion). The MeOH conversion increased upon addition of metal oxides in the order CaO 〉〉 MgO 〉 ZnO, with the DMC selectivity (SDMC) following the order MgO 〉 CaO 〉 ZnO. The catalysts and dehydrating agents were characterized before and after the oxidative carbonylation of methanol by thermogravimetric and differential thermogravimetric (TG/DTG), and XRD to con- firm that the dehydration reaction occurred via the metal oxide (MO + H2O →M(OH)2). The MeOH conversion increased from 8.7% to 14.6% and DMC selectivity increased from 39.0% to 53.1%, when using the dehydrating azent CaO.
基金supported by the National Key Research and Development Program(2017YFC0306403)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA09030104,XDA22010601)the Youth Innovation Promotion Association of the Chinese Academy of Sciences~~
文摘Hydrogen is a promising sustainable energy to replace fossil fuels owning to its high specific energy and environmental friendliness.Alkaline water electrolysis has been considered as one of the most prospective technologies for large scale hydrogen production.To boost the sluggish kinetics of hydrogen evolution reaction(HER)in alkaline media,abundant materials have been designed and fabricated.Herein,we summarize the key achievements in the development of layered transition-metal hydroxides[TM(OH)x]for efficient alkaline HER.Based on the structure of TM(OH)x,the mechanism of synergistic effect between TM(OH)x and HER active materials is illuminated firstly.Then,recent progress of TM(OH)x-based HER catalysts to optimize the synergistic effect are categorized as TM(OH)x and active materials,including species,structure,morphology and interaction relationship.Furthermore,TM(OH)x-based overall water splitting electrocatalysts and electrodes are summarized in the design principles for high activity and stability.Finally,some of key challenges for further developments and applications of hydrogen production are proposed.
文摘Promoted by active indium produced in situ by Sm/InCl3 ?4H2O system, arylidenecyano- acetates undergo reductive cyclodimerization to afford cyclopentamine derivatives with high stereoselectivity under mild conditions in aqueous media.
基金Supported by the Iranian Nano Technology Initiative Council and Petroleum University of Technology
文摘In reverse water gas shift (RWGS) reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, inductively coupled plasma atomic emission spectrometer (ICP-AES), temperature programmed reduction (H2-TPR), CO chemisorption, energy dispersive X-ray (EDX) and scanning electron microscopy (SEM) techniques. Kinetic properties of all catalysts were investigated in a batch re- actor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/AlzO3 catalyst enhances its activity as compared to Fe/AlaO3. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/AlzO3 catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fez(MoO4)3 phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fez(MoO4)3 phase has low reducibility, therefore the Fe2(MoO4)3 phase significantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al2O3 catalyst. Overall, this study introduces Fe-Mo/Al2O3 as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.
文摘The feasibility of rhenium (Re) production by irradiating tungsten (W) metal in a medium size fast reactor was evaluated by using a Monte Carlo code. The fast reactor can produce about 50 kilograms of Re per every 3 years, which corresponds 10% of Japanese domestic production. The specific activity of Re can be reduced below the exemption level or even the natural Re level if W and osmium is separated after the irradiation. The use of ZrD1.7 moderator reduces the specific activity by half compared to that of ZrH1.7 case, and even the no moderator case is permissible to produce the production of Re which has lower specific reactivity than that of natural Re.
基金the Iranian Nano Technology Initiative Council and the Petroleum University of Technology for financial support
文摘The performance of the two newly developed bimetallic catalysts based on the precursor, Mo/Al_2O_3, was compared for reverse water gas shift(RWGS) reaction. The structures of the precursor and the catalysts were studied using X-ray diffraction(XRD), Brunauer–Emmett–Teller(BET) analysis, inductively coupled plasma-atomic emission spectrometry(ICP-AES), CO chemisorption, temperature programmed reduction of hydrogen(H_2-TPR) and scanning electron microscopy(SEM) techniques. The activity of Fe-Mo and Co-Mo catalysts was compared in a fixed bed reactor at different temperatures. It is shown that the Co-Mo catalyst has higher CO_2 conversion at all temperature level. The time-on-stream(TOS) analysis of the activity of catalysts for the RWGS reaction was carried out over a continuous period of 60h for both catalysts. The Fe-Mo/Al_2O_3 catalyst exhibits good stability within a period of 60h, however, the Co-Mo/Al_2O_3 is gradually deactivated after 50h of reaction time. Existence of(Fe_2(MoO4_))_3 phase in Fe-Mo/Al_2O_3 catalyst makes this catalyst more stable for RWGS reaction.
基金supported by the National Basic Research Program of China(2016YFA0602900)Youth Innovation Promotion Association CAS(2016206)Jilin Provincial Science and Technology Program of China(20150301012GX)
文摘Hexamethylenediamine(HMDA) is an important reagent for the synthesis of Nylon-6,6, and it is usually produced by the hydrogenation of adiponitrile using a toxic reagent of hydrocyanic acid. Herein, we developed an environmental friendly route to produce HMDA via catalytic reductive amination of 1,6-hexanediol(HDO) in the presence of hydrogen. The activities of several heterogeneous metal catalysts such as supported Ni, Co, Ru, Pt, Pd catalysts were screened for the present reaction in supercritical ammonia without any additives. Among the catalysts examined, Ru/Al_2O_3 presented a high catalytic activity and highest selectivity for the desired product of HMDA. The high performance of Ru/Al_2O_3 was discussed based on the Ru dispersion and the surface properties like the acid-basicity. In addition, the reaction parameters such as reaction temperature,time, H_2 and NH_3 pressure were examined, and the reaction processes were discussed in detail.
基金financially supported by the National Natural Science Foundation of China (21035005)
文摘Carbon dots (CDs) with average diameter of 3.1 ± 0.5 nm were facilely synthesized with candle soot through hydrothermal reaction in sodium hydroxide aqueous solution. The as-prepared CDs were covered with a lot of hydroxyls, possessed properties of good water-solubility, anti-photobleaching, salt tolerance, and low cytotoxicity, and had a fluorescence quantum yield (QY) of about 5.5%. The fluorescence of the hydroxyls-coated CDs could be selectively quenched by metal ions such as Cr3+, Al3+ and Fe3+, which is because these metals can easily combine with the hydroxyl groups on the surface of CDs and induce aggregation of hydroxyls-coated CDs. Experiments showed that the quenching of Cr3+ had a Sterm-Volmer constant of 1.03 × 107 M-1 with a liner range of 1.0-25.0 μM and detection limit of 60 nM (3σ).
基金supported by the National Natural Science Foundation of Chinathe National Key Research and Development Project (2018YFB1502401)+4 种基金the Royal Society and Newton Fund through Newton Advanced Fellowship award (NAF\R1\191294)the Program for Changjiang Scholars and Innovative Research Team in the Universitythe Fundamental Research Funds for the Central Universitiesthe Longterm Subsidy Mechanism from the Ministry of Finance and the Ministry of Education of Chinathe financial support from China Scholarships Council (CSC)
文摘Development of highly active electrocatalysts for oxygen evolution reaction(OER)is one of the critical issues for water splitting,and most reported catalysts operate at overpotentials above 190 mV.Here we present a multiphase nickel iron sulfide(MPS)hybrid electrode with a hierarchical structure of iron doped NiS and Ni3S2,possessing a benchmark OER activity in alkaline media with a potential as low as 1.33 V(vs.reversible hydrogen electrode)to drive an OER current density of 10 mA cm^-2.The Fe doped NiS,combined with highly conductive disulfide phase on porous Ni foam,is believed to be responsible for the ultrahigh activity.Furthermore,density functional theory simulation reveals that partially oxidized sulfur sites in Fe doped NiS could dramatically lower the energy barrier for the rate-determining elementary reaction,thus contributing to the active oxygen evolution.