Cu nanoparticles supported on a variety of oxide supports, including SiO2, TiO2, ZrO2, Al2O3, MgO and ZnO, were investigated for the hydrogenolysis of biomass‐derived furfuryl alcohol to1,2‐pentanediol and 1,5‐pent...Cu nanoparticles supported on a variety of oxide supports, including SiO2, TiO2, ZrO2, Al2O3, MgO and ZnO, were investigated for the hydrogenolysis of biomass‐derived furfuryl alcohol to1,2‐pentanediol and 1,5‐pentanediol. A Cu‐Al2O3 catalyst with 10 wt% Cu loading prepared by a co‐precipitation method exhibited the best performance in terms of producing pentanediols compared with the other materials. This catalyst generated an 85.8% conversion and a 70.3% combined selectivity for the target pentanediols at 413 K and 8 MPa H2 over an 8‐h reaction. The catalyst could also be recycled over repeated reaction trials without any significant decrease in productivity. Characterizations with X‐ray diffraction, NH3/CO2‐temperature programmed desorption, N2 adsorption,transmission electron microscopy and N2 O chemisorption demonstrated that intimate and effective interactions between Cu particles and the acidic Al2O3 support in this material greatly enhanced its activity and selectivity. The promotion of the hydrogenolysis reaction was found to be especially sensitive to the Cu particle size, and the catalyst with Cu particles 1.9 to 2.4 nm in size showed the highest turnover frequency during the synthesis of pentanediols.展开更多
Selective hydrogenolysis of biomass‐derived furfuryl alcohol(FFA)to 1,5‐and 1,2‐pentanediol(PeD)was conducted over Cu‐LaCoO3 catalysts with different Cu loadings;the catalysts were derived from perovskite structur...Selective hydrogenolysis of biomass‐derived furfuryl alcohol(FFA)to 1,5‐and 1,2‐pentanediol(PeD)was conducted over Cu‐LaCoO3 catalysts with different Cu loadings;the catalysts were derived from perovskite structures prepared by a one‐step citrate complexing method.The catalytic performances of the Cu‐LaCoO3 catalysts were found to depend on the Cu loading and pretreatment conditions.The catalyst with 10 wt%Cu loading exhibited the best catalytic performance after prereduction in 5%H2‐95%N2,achieving a high FFA conversion of 100%and selectivity of 55.5%for 1,5‐pentanediol(40.3%)and 1,2‐pentanediol(15.2%)at 413 K and 6 MPa H2.This catalyst could be reused four times without a loss of FFA conversion but it resulted in a slight decrease in pentanediol selectivity.Correlation between the structural changes in the catalysts at different states and the simultaneous variation in the catalytic performance revealed that cooperative catalysis between Cu0 and CoO promoted the hydrogenolysis of FFA to PeDs,especially to 1,5‐PeD,while Co0 promoted the hydrogenation of FFA to tetrahydrofurfuryl alcohol(THFA).Therefore,it is suggested that a synergetic effect between balanced Cu0 and CoO sites plays a critical role in achieving a high yield of PeDs with a high 1,5‐/1,2‐pentanediol selectivity ratio during FFA hydrogenolysis.展开更多
In this work, MoOx promoted Ir/SiO2 catalysts were prepared and used for the selective hydrogenolysis of tetrahydrofurfuryl alcohol （THFA） to 1,5-pentanediol in a continuous flow reactor. The effects of different no...In this work, MoOx promoted Ir/SiO2 catalysts were prepared and used for the selective hydrogenolysis of tetrahydrofurfuryl alcohol （THFA） to 1,5-pentanediol in a continuous flow reactor. The effects of different noble metals （Ir, Pt, Pd, Ru, Rh）, supports and Ir contents were screened. Among the investigated catalysts, 4 wt%Ir-MoOx/SiO2 with a Mo/Ir atomic ratio of 0.13 exhibited the best catalytic performance. The synergy between Ix particles and the partially reduced isolated MoOx species attached on them is essential for the excellent catalytic performance of Ix-MoOx/SiO2. The catalyst exhibited a better hydrogenolysis efficiency of THFA with the selectivity of 1,5-pentanediol of 65%-74% at a conversion of THFA of 70%-75% when the initial THFA concentration is ranging from 20 wt% and 40 wt%. And higher system pressure was also in favor of the conversion of THFA. During a stability test, the conversion of THFA and 1,5-pentanediol yield over Ix-MoOz/SiO2 decreased with reaction time, which can be explained by the leaching of Mo species during the reaction.展开更多
The selective hydrogenolysis of glycerol exhibits great prospects,while the catalysts with high selectivity and activity are still missing and need to be created urgently.Herein,we report the synthesis of hollow mesop...The selective hydrogenolysis of glycerol exhibits great prospects,while the catalysts with high selectivity and activity are still missing and need to be created urgently.Herein,we report the synthesis of hollow mesoporous Pt/WO_(x)/SiO_(2)-TiO_(2)nanosphere catalysts with bi-functional interfaces synergistically for high efficiency conversion of glycerol to 1,3-propanediol.The hollow mesoporous Pt/WO_(x)/SiO_(2)-TiO_(2)catalysts show a typical brick-concrete liked framework with a high surface area(179.3 m^(2)·g^(-1)),large mesopore size(10.6 nm),uniform particle size(~400 nm),and ultrathin shell thickness(~75 nm).The brick anatase nanocrystals and concrete amorphous SiO_(2)networks can selectively rivet Pt nanoparticles and WO_(x)nanocluster species,respectively,thus constructing two interfaces for effective adsorption,rapidly catalytic dehydration and hydrogenation processes.The hollow mesoporous Pt/WO_(x)/SiO_(2)-TiO_(2)catalysts deliver a high selectivity of 53.8%for 1,3-propanediol(1,3-PDO)at a very high glycerol conversion of 85.0%.As a result,a favorable 1,3-PDO yield of 45.7%can be obtained with excellent stability,which is among the best performances of previously reported catalysts.This work paves a new way to synthesize catalysts with high selectivity,high activity and high stability.展开更多
基金supported by the National Natural Science Foundation of China(2113301121203221+1 种基金21473224)the Natural Science Foundation of Gansu Province(1308RJZA281)~~
文摘Cu nanoparticles supported on a variety of oxide supports, including SiO2, TiO2, ZrO2, Al2O3, MgO and ZnO, were investigated for the hydrogenolysis of biomass‐derived furfuryl alcohol to1,2‐pentanediol and 1,5‐pentanediol. A Cu‐Al2O3 catalyst with 10 wt% Cu loading prepared by a co‐precipitation method exhibited the best performance in terms of producing pentanediols compared with the other materials. This catalyst generated an 85.8% conversion and a 70.3% combined selectivity for the target pentanediols at 413 K and 8 MPa H2 over an 8‐h reaction. The catalyst could also be recycled over repeated reaction trials without any significant decrease in productivity. Characterizations with X‐ray diffraction, NH3/CO2‐temperature programmed desorption, N2 adsorption,transmission electron microscopy and N2 O chemisorption demonstrated that intimate and effective interactions between Cu particles and the acidic Al2O3 support in this material greatly enhanced its activity and selectivity. The promotion of the hydrogenolysis reaction was found to be especially sensitive to the Cu particle size, and the catalyst with Cu particles 1.9 to 2.4 nm in size showed the highest turnover frequency during the synthesis of pentanediols.
文摘Selective hydrogenolysis of biomass‐derived furfuryl alcohol(FFA)to 1,5‐and 1,2‐pentanediol(PeD)was conducted over Cu‐LaCoO3 catalysts with different Cu loadings;the catalysts were derived from perovskite structures prepared by a one‐step citrate complexing method.The catalytic performances of the Cu‐LaCoO3 catalysts were found to depend on the Cu loading and pretreatment conditions.The catalyst with 10 wt%Cu loading exhibited the best catalytic performance after prereduction in 5%H2‐95%N2,achieving a high FFA conversion of 100%and selectivity of 55.5%for 1,5‐pentanediol(40.3%)and 1,2‐pentanediol(15.2%)at 413 K and 6 MPa H2.This catalyst could be reused four times without a loss of FFA conversion but it resulted in a slight decrease in pentanediol selectivity.Correlation between the structural changes in the catalysts at different states and the simultaneous variation in the catalytic performance revealed that cooperative catalysis between Cu0 and CoO promoted the hydrogenolysis of FFA to PeDs,especially to 1,5‐PeD,while Co0 promoted the hydrogenation of FFA to tetrahydrofurfuryl alcohol(THFA).Therefore,it is suggested that a synergetic effect between balanced Cu0 and CoO sites plays a critical role in achieving a high yield of PeDs with a high 1,5‐/1,2‐pentanediol selectivity ratio during FFA hydrogenolysis.
基金supported by the National Natural Science Foundation of China(No.21106143,No.21277140)100-Talent Project of Dalian Institute of Chemical Physics(DICP)+1 种基金the Independent Innovation Foundation of State Key Laboratory of Catalysis(No.R201113)the Zhejiang Provincial Natural Science Foundation of China(LR12E02001)
文摘In this work, MoOx promoted Ir/SiO2 catalysts were prepared and used for the selective hydrogenolysis of tetrahydrofurfuryl alcohol （THFA） to 1,5-pentanediol in a continuous flow reactor. The effects of different noble metals （Ir, Pt, Pd, Ru, Rh）, supports and Ir contents were screened. Among the investigated catalysts, 4 wt%Ir-MoOx/SiO2 with a Mo/Ir atomic ratio of 0.13 exhibited the best catalytic performance. The synergy between Ix particles and the partially reduced isolated MoOx species attached on them is essential for the excellent catalytic performance of Ix-MoOx/SiO2. The catalyst exhibited a better hydrogenolysis efficiency of THFA with the selectivity of 1,5-pentanediol of 65%-74% at a conversion of THFA of 70%-75% when the initial THFA concentration is ranging from 20 wt% and 40 wt%. And higher system pressure was also in favor of the conversion of THFA. During a stability test, the conversion of THFA and 1,5-pentanediol yield over Ix-MoOz/SiO2 decreased with reaction time, which can be explained by the leaching of Mo species during the reaction.
基金This work was supported by the National Key R&D Program of China(Nos.2022YFA1503501 and 2018YFA0209401)the National Natural Science Foundation of China(Nos.22088101,21975050 and U21A20329)+2 种基金the Program of Shanghai Academic Research Leader(No.21XD1420800)the Shanghai Pilot Program for Basic Research-Fudan University 21TQ1400100(No.21TQ008)the Fundamental Research Funds for the Central Universities(No.20720220010).
文摘The selective hydrogenolysis of glycerol exhibits great prospects,while the catalysts with high selectivity and activity are still missing and need to be created urgently.Herein,we report the synthesis of hollow mesoporous Pt/WO_(x)/SiO_(2)-TiO_(2)nanosphere catalysts with bi-functional interfaces synergistically for high efficiency conversion of glycerol to 1,3-propanediol.The hollow mesoporous Pt/WO_(x)/SiO_(2)-TiO_(2)catalysts show a typical brick-concrete liked framework with a high surface area(179.3 m^(2)·g^(-1)),large mesopore size(10.6 nm),uniform particle size(~400 nm),and ultrathin shell thickness(~75 nm).The brick anatase nanocrystals and concrete amorphous SiO_(2)networks can selectively rivet Pt nanoparticles and WO_(x)nanocluster species,respectively,thus constructing two interfaces for effective adsorption,rapidly catalytic dehydration and hydrogenation processes.The hollow mesoporous Pt/WO_(x)/SiO_(2)-TiO_(2)catalysts deliver a high selectivity of 53.8%for 1,3-propanediol(1,3-PDO)at a very high glycerol conversion of 85.0%.As a result,a favorable 1,3-PDO yield of 45.7%can be obtained with excellent stability,which is among the best performances of previously reported catalysts.This work paves a new way to synthesize catalysts with high selectivity,high activity and high stability.
