Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to ethylene(C_(2)H_(4))represents a promising approach to reducing CO_(2)emissions and producing high-value chemicals.The ethylene productivity is always limited by t...Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to ethylene(C_(2)H_(4))represents a promising approach to reducing CO_(2)emissions and producing high-value chemicals.The ethylene productivity is always limited by the slow reaction kinetics and the high-performance catalysts are significantly desired.Many efforts have been made to develop a catalyst to activate CO_(2)molecules.However,as another reactant,H2O activation does not receive the attention it deserves.In particular,slow H2O dissociation kinetics limit the rate of proton supply,severely impairing the production of C_(2)H_(4).Here,we designed a MgO-modified CuO catalyst(MgO/CuO),which can promote H2O dissociation and enhance CO_(2)adsorption at the same time to realize the efficient ethylene production.The optimal catalyst exhibits a Faraday efficiency for C_(2)H_(4)reached 54.4%at−1.4 V vs.RHE in an H-cell,which is 1.4 times that of pure CuO(37.9%),and it was further enhanced to a 56.7%in a flow cell,with a high current density of up to 535.9 mA cm−2 at−1.0 V vs.RHE.Experimental and theoretical calculations show that MgO/CuO plays a bifunctional role in the CO_(2)RR,which facilitates the adsorption and activation of CO_(2)by CuO and simultaneously accelerates H2O dissociation by MgO doping.The in situ XRD experiments demonstrate that the introduction of MgO protects CuO active phase to avoid overreduction and preserves the active centers for CO_(2)RR.In combination with in situ FTIR and DFT calculations,the protonation process from*CO to*COH and asymmetric C–C coupling step are promoted by the enhanced water activation and proton coupling on MgO/CuO.This work provides new insights into the CO_(2)and H_(2)O coactivation mechanism in CO_(2)RR and a potential universal strategy to design ethylene production electrocatalysts.展开更多
Activities of FeO in CaO-SiO2-Al2O3-MgO-FeO slags were determined at 1673 K by electrochemical of the solid electrolyte cell： Mo [Mo＋MoOu[ZrO2（MgO）[Fe＋（CaO-SiO2-Al2O3-MgO-FeO）＋Ag[Fe. The influences of slag com...Activities of FeO in CaO-SiO2-Al2O3-MgO-FeO slags were determined at 1673 K by electrochemical of the solid electrolyte cell： Mo [Mo＋MoOu[ZrO2（MgO）[Fe＋（CaO-SiO2-Al2O3-MgO-FeO）＋Ag[Fe. The influences of slag compositions and basicity on FeO activities were analyzed. The results reveal that, for slags of fixed （%CaO）/（%SiO2） ratio, MgO and Al2O3 content, there was an increase of FeO activities with increase of FeO content. For slags with constant {（%CaO）＋ （%MgO）}/（%SiO2） ratio, fixed FeO and A1203 content, FeO activities decreased when MgO content increased from 5% to 10%, and increased with the increase of MgO content when it was over 10%. The FeO activities increased when （%CaO）/（%SiO2） ratio changed from 1.03 to 1.30 in the slags of constant MgO, FeO and Al2O3 content.展开更多
The activity of MgO in MgO-B2O_3 melt was experimentally determined at 1773 and 1823 K by means of slag-liquid Sn equilibrium.The activity of B_2O_3 was calculated by integrating Gibbs-Duhem equation.The standard Gibb...The activity of MgO in MgO-B2O_3 melt was experimentally determined at 1773 and 1823 K by means of slag-liquid Sn equilibrium.The activity of B_2O_3 was calculated by integrating Gibbs-Duhem equation.The standard Gibbs energies of formation of binary compounds 2MgOB_2O_3 and 3MgO·B_2O_3 were estimated with the activity data of components in B_2O_3-MgO melt.展开更多
Ceramic dielectric materials with high dielectric strength and mechanisms of their internal factors affecting dielectric strength are significantly valuable for industrial application,especially for selection of suita...Ceramic dielectric materials with high dielectric strength and mechanisms of their internal factors affecting dielectric strength are significantly valuable for industrial application,especially for selection of suitable dielectric materials for high-power microwave transmission devices and reliable power transmission.Pure magnesium oxide(MgO),a kind of ceramic dielectric material,possesses great application potential in high-power microwave transmission devices due to its high theoretical dielectric strength,low dielectric constant,and low dielectric loss properties,but its application is limited by high sintering temperature during preparation.This work presented the preparation of a new type of multiphase ceramics based on MgO,which was MgO-1%ZrO_(2)-1%CaCO_(3-x)%MnCO_(3)(MZCM_(x),x=0,0.25,0.50,1.00,1.50,in molar),and their phase structures,morphological features,and dielectric properties were investigated.It was found that inclusion of ZrO_(2) and CaCO_(3) effectively inhibited excessive growth of MgO grains by formation of second phase,while addition of MnCO_(3) promoted the grain boundary diffusion process during the sintering process and reduced activation energy for the grain growth,resulting in a lower ceramic sintering temperature.Excellent performance,including high dielectric strength(Eb=92.3 kV/mm)and quality factor(Q×f=216642 GHz),simultaneously accompanying low dielectric loss(<0.03%),low temperature coefficient of dielectric constant(20.3×10^(–6)℃^(–1),85℃)and resonance frequency(–12.54×10^(–6)℃^(–1)),was achieved in MZCM1.00 ceramics under a relatively low sintering temperature of 1350℃.This work offers an effective solution for selecting dielectric materials for high-power microwave transmission devices.展开更多
文摘为抑制碱激发胶凝材料(AASM)因水化反应集中、孔隙失水引起的显著自收缩,本文提出采用MgO与Na_(2)SiO_(3)复配为复合激发剂,系统研究其对AASM凝结行为、水化产物组成、孔结构特征、强度发展与自收缩性能的影响规律。通过XRD(X-ray diffraction)与NMR(nuclear magnetic resonance)等手段表征发现:随着复合激发剂中MgO比例的增加,体系内类水滑石相生成显著增多,同时最可几孔径向10~20 nm区间集中,孔隙率有所上升。上述微观结构演变导致以下宏观性能变化:一方面,MgO的弱碱性质延缓了矿渣的水化进程,凝结时间延长,抗压强度随其掺量增加而降低;另一方面,类水滑石相的体积膨胀效应与孔隙率的提高共同缓解了毛细孔应力,使AASM的自收缩显著减小。研究表明,MgO与Na_(2)SiO_(3)在调控反应进程与水化产物组成方面具有协同作用。Na_(2)SiO_(3)提供强碱性环境以保障早期强度发展,而MgO则通过促进膨胀性产物生成,优化孔隙结构,有效抑制收缩开裂。该复合激发策略为兼顾AASM力学性能与体积稳定性提供了可行途径。
基金supported by the National Natural Science Foundation of China(Grant No.U21B2099,U22A20425,and 22208377)Natural Science Foundation of Shandong Province(ZR2021QE062)Fundamental Research Funds for the Central Universities,Ocean University of China(grant number 202364004)。
文摘Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to ethylene(C_(2)H_(4))represents a promising approach to reducing CO_(2)emissions and producing high-value chemicals.The ethylene productivity is always limited by the slow reaction kinetics and the high-performance catalysts are significantly desired.Many efforts have been made to develop a catalyst to activate CO_(2)molecules.However,as another reactant,H2O activation does not receive the attention it deserves.In particular,slow H2O dissociation kinetics limit the rate of proton supply,severely impairing the production of C_(2)H_(4).Here,we designed a MgO-modified CuO catalyst(MgO/CuO),which can promote H2O dissociation and enhance CO_(2)adsorption at the same time to realize the efficient ethylene production.The optimal catalyst exhibits a Faraday efficiency for C_(2)H_(4)reached 54.4%at−1.4 V vs.RHE in an H-cell,which is 1.4 times that of pure CuO(37.9%),and it was further enhanced to a 56.7%in a flow cell,with a high current density of up to 535.9 mA cm−2 at−1.0 V vs.RHE.Experimental and theoretical calculations show that MgO/CuO plays a bifunctional role in the CO_(2)RR,which facilitates the adsorption and activation of CO_(2)by CuO and simultaneously accelerates H2O dissociation by MgO doping.The in situ XRD experiments demonstrate that the introduction of MgO protects CuO active phase to avoid overreduction and preserves the active centers for CO_(2)RR.In combination with in situ FTIR and DFT calculations,the protonation process from*CO to*COH and asymmetric C–C coupling step are promoted by the enhanced water activation and proton coupling on MgO/CuO.This work provides new insights into the CO_(2)and H_(2)O coactivation mechanism in CO_(2)RR and a potential universal strategy to design ethylene production electrocatalysts.
基金Project supported by the National Natural Science Foundation of China （Grant No.50574036）
文摘Activities of FeO in CaO-SiO2-Al2O3-MgO-FeO slags were determined at 1673 K by electrochemical of the solid electrolyte cell： Mo [Mo＋MoOu[ZrO2（MgO）[Fe＋（CaO-SiO2-Al2O3-MgO-FeO）＋Ag[Fe. The influences of slag compositions and basicity on FeO activities were analyzed. The results reveal that, for slags of fixed （%CaO）/（%SiO2） ratio, MgO and Al2O3 content, there was an increase of FeO activities with increase of FeO content. For slags with constant {（%CaO）＋ （%MgO）}/（%SiO2） ratio, fixed FeO and A1203 content, FeO activities decreased when MgO content increased from 5% to 10%, and increased with the increase of MgO content when it was over 10%. The FeO activities increased when （%CaO）/（%SiO2） ratio changed from 1.03 to 1.30 in the slags of constant MgO, FeO and Al2O3 content.
文摘The activity of MgO in MgO-B2O_3 melt was experimentally determined at 1773 and 1823 K by means of slag-liquid Sn equilibrium.The activity of B_2O_3 was calculated by integrating Gibbs-Duhem equation.The standard Gibbs energies of formation of binary compounds 2MgOB_2O_3 and 3MgO·B_2O_3 were estimated with the activity data of components in B_2O_3-MgO melt.
基金Student Training Program for Innovation and Entrepreneurship of Hangzhou Institute for Advanced Study,UCAS(CXCY20230305)Chinese Academy of Sciences Key Project(ZDRW-CN-2021-3-1-18)。
文摘Ceramic dielectric materials with high dielectric strength and mechanisms of their internal factors affecting dielectric strength are significantly valuable for industrial application,especially for selection of suitable dielectric materials for high-power microwave transmission devices and reliable power transmission.Pure magnesium oxide(MgO),a kind of ceramic dielectric material,possesses great application potential in high-power microwave transmission devices due to its high theoretical dielectric strength,low dielectric constant,and low dielectric loss properties,but its application is limited by high sintering temperature during preparation.This work presented the preparation of a new type of multiphase ceramics based on MgO,which was MgO-1%ZrO_(2)-1%CaCO_(3-x)%MnCO_(3)(MZCM_(x),x=0,0.25,0.50,1.00,1.50,in molar),and their phase structures,morphological features,and dielectric properties were investigated.It was found that inclusion of ZrO_(2) and CaCO_(3) effectively inhibited excessive growth of MgO grains by formation of second phase,while addition of MnCO_(3) promoted the grain boundary diffusion process during the sintering process and reduced activation energy for the grain growth,resulting in a lower ceramic sintering temperature.Excellent performance,including high dielectric strength(Eb=92.3 kV/mm)and quality factor(Q×f=216642 GHz),simultaneously accompanying low dielectric loss(<0.03%),low temperature coefficient of dielectric constant(20.3×10^(–6)℃^(–1),85℃)and resonance frequency(–12.54×10^(–6)℃^(–1)),was achieved in MZCM1.00 ceramics under a relatively low sintering temperature of 1350℃.This work offers an effective solution for selecting dielectric materials for high-power microwave transmission devices.
