Electrochemical reduction of CO_(2)into high-value hydrocarbons and alcohols by using Cu-based catalysts is a promising and attractive technology for CO_(2)capture and utilization,resulting from their high catalytic a...Electrochemical reduction of CO_(2)into high-value hydrocarbons and alcohols by using Cu-based catalysts is a promising and attractive technology for CO_(2)capture and utilization,resulting from their high catalytic activity and selectivity.The mobility and accessibility of active sites in Cubased catalysts significantly hinder the development of efficient Cu-based catalysts for CO_(2)electrochemical reduction reaction(CO_(2)RR).Herein,a facile and effective strategy is developed to engineer accessible and structural stable Cu sites by incorporating single atomic Cu into the nitrogen cavities of the host graphitic carbon nitride(g-C_(3)N_(4))as the active sites for CO_(2)-to-CH_(4)conversion in CO_(2)RR.By regulating the coordination and density of Cu sites in g-C_(3)N_(4),an optimal catalyst corresponding to a one Cu atom in one nitrogen cavity reaches the highest CH_(4)Faraday efficiency of 49.04%and produces the products with a high CH_(4)/C_(2)H_(4)ratio over 9.This work provides the first experimental study on g-C_(3)N_(4)-supported single Cu atom catalyst for efficient CH_(4)production from CO_(2)RR and suggests a principle in designing highly stable and selective high-efficiency Cu-based catalysts for CO_(2)RR by engineering Cu active sites in 2D materials with porous crystal structures.展开更多
Localized CdS homojunctions with optimal ratio of high and low index facets are constructed to dy-namically boost H_(2)O splitting into H_(2)energy by hydrothermal method in combination with calcination.By density fun...Localized CdS homojunctions with optimal ratio of high and low index facets are constructed to dy-namically boost H_(2)O splitting into H_(2)energy by hydrothermal method in combination with calcination.By density functional theory,hall effect,and in situ diffuse reflectance infrared Fourier transform spec-troscopy,it is revealed that photo-irradiated e^(−)and h^(+)can be spatially separated and directionally trans-ferred to the reductive high-index facet{002}and oxidative low-index facet{110}of localized CdS homo-junction induced by Fermi level difference of both high and low index facets to dehydrogenate ^(∗)-OH and coupled ^(∗)-O intermediates for H_(2)and O_(2)yield,respectively,along with a solar conversion into hydrogen of 1.93%by AM 1.5 G irradiation at 65℃.The study work suggests a scientific perspective on the optimal ratio of high and low index facets to understand photo-generated charge carrier transfer dynamically and their photocatalytic principle for H_(2)O splitting reaction in kinetics.展开更多
We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,ind...We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,indicating that Raman quantification of CH4/CO2 molar ratio can be applied to those fluid inclusions(FIs)with high internal pressure(i.e.,>15 MPa).Secondly,the v1(CH4)peak position shifts to lower wavenumber with increasing pressure at constant temperature,confirming that the v1(CH4)peak position can be used to calculate the fluid pressure.However,this method should be carefully calibrated before applying to FI analyses because large discrepancies exist among the reported v1(CH4)-P curves,especially in the highpressure range.These calibrations are applied to CH4-rich FIs in quartz veins of the Silurian Longmaxi black shales in southern Sichuan Basin.The vapor phases of these FIs are mainly composed of CH4 and minor CO2,with CO2 molar fractions from4.4%to 7.4%.The pressure of single-phase gas FI ranges from 103.65 to 128.35 MPa at room temperature,which is higher than previously reported.Thermodynamic calculations supported the presence of extremely high-pressure CH4-saturated fluid(218.03–256.82 MPa at 200°C),which may be responsible for the expulsion of CH4 to adjacent reservoirs.展开更多
Dimethoxymethane(DMM),a diesel blend fuel,is being researched with high interest recently due to its unique fuel properties.It is commercially produced via a two step-process of methanol oxidation to make formaldehyde...Dimethoxymethane(DMM),a diesel blend fuel,is being researched with high interest recently due to its unique fuel properties.It is commercially produced via a two step-process of methanol oxidation to make formaldehyde,followed by its condensation with methanol.This study presents a one-pot method of DMM synthesis from methanol mediated carbon dioxide hydrogenation over novel heterogeneous catalysts.The effect of catalyst pore structure was investigated by synthesizing 3 wt%Ru over novel hierarchical zeolite beta(HBEASX)and comparing against Ru doped commercial zeolite beta(CBEA)and desilicated hierarchical zeolite beta(HBZDS).The results showed that 3%Ru/HBEASX provided the best activity for DMM production due to its large average pore size.It also showed the decisive role of SiO_(2)/Al_(2)O_(3)molar ratio,with SiO_(2)/Al_(2)O_(3)=75 providing the highest DMM yield of 13.2 mmol/gcat.LMeOH with ca.100%selectivity.The activity of 3%Ru/HBEAS3 after 5 recycle steps demonstrated the reusability of this catalyst.展开更多
We demonstrate here that global-scale determination of a key ionospheric parameter,the peak height of the F_(2)region(h_(m)F_(2)),can be obtained by making a simple ratio measurement of the atomic oxygen 130.4 and 135...We demonstrate here that global-scale determination of a key ionospheric parameter,the peak height of the F_(2)region(h_(m)F_(2)),can be obtained by making a simple ratio measurement of the atomic oxygen 130.4 and 135.6 nm emissions in the far-ultraviolet nightglow with a nadir-viewing system such as a pair of photometers suitable for flight on a CubeSat.We further demonstrate that measurements from an altitude that is within the typical range of nighttime h_(m)F_(2)250−450 km can provide the ratios that are needed for retrieval of the h_(m)F_(2).Our study is conducted mostly through numerical simulations by using radiative transfer models of the two emissions coupled with empirical models of the atmosphere and ionosphere.Modeling results show that the relationship between the h_(m)F_(2)and the intensity ratio is sensitive to the altitude from which the emissions are observed,primarily because of the distinctly different degrees of resonant scattering of the two emissions in the atmosphere.A roughly quadratic relationship can be established for observations from an orbit of~400 km,which enables h_(m)F_(2)retrieval.Parametric analysis indicates that the relationship can be affected by the ambient atmospheric conditions through resonant scattering and O2 absorption.For typical nighttime conditions with h_(m)F_(2)250−450 km,retrieval of the h_(m)F_(2)from synthetic observations shows that the typical errors are only a few kilometers(up to~20 km),depending on the accuracy of the ambient conditions predicted by the empirical models.Our findings pave the way for use of the 130.4/135.6 nm intensity ratios for global-scale monitoring of the nighttime ionosphere at mid to low latitudes.展开更多
It is urgent to develop excellent solid CO<sub>2</sub> sorbents with higher sorption capacity, simpler synthetic process, better thermal stability and lower costs of synthesis in CO<sub>2</sub>...It is urgent to develop excellent solid CO<sub>2</sub> sorbents with higher sorption capacity, simpler synthetic process, better thermal stability and lower costs of synthesis in CO<sub>2</sub> capture and storage technologies. In this work, a number of Li<sub>4</sub>SiO<sub>4</sub>-based sorbents synthesized by lithium carbonate with three different kinds of fly ashes in various molar ratios were developed. The results indicate that the Li<sub>2</sub>CO<sub>3</sub>:SiO<sub>2</sub> mole ratio used in the sorbents synthesis significantly affects the CO<sub>2</sub> absorption properties. The sorption capacity increased with the excess of Li<sub>2</sub>CO<sub>3</sub> first and then decreased when the excessive quantity was beyond a certain amount. The experiments found that FA-Li<sub>4</sub>SiO<sub>4</sub>_0.6, CFA-Li<sub>4</sub>SiO<sub>4</sub>_0.4, HCl/CFA-Li<sub>4</sub>SiO<sub>4</sub>_0.3 presented the best sorption ability among these fly ash derived Li<sub><span style="font-family:Verdana;">4</span></sub><span style="font-family:Verdana;">SiO</span><sub><span style="font-family:Verdana;">4</span></sub><span style="font-family:Verdana;"> samples, and the corresponding weight gain was 28.2 wt%, 25.1 wt% and 32.5 wt%, respectively. The three sorbents with the optimal molar ratio were characterized using various morphological </span><span style="font-family:Verdana;">characterization techniques and evaluated by thermogravimetric analysis </span><span style="font-family:Verdana;">for their capacity to chemisorb CO<sub>2</sub> at 450<sup></sup></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;"><span style="font-family:Verdana, Helvetica, Arial;white-space:normal;background-color:#FFFFFF;">°</span></span><span style="font-family:Verdana;"></span><span style="font-family:Verdana;">C</span><span style="font-family:Verdana;"> - 650<sup></sup></span><span style="font-family:Verdana;"><span style="font-family:Verdana, Helvetica, Arial;white-space:normal;background-color:#FFFFFF;">°</span></span><span style="font-family:Verdana;"></span><span style="font-family:Verdana;">C</span><span style="font-family:Verdana;">, diluted CO<sub>2</sub> (10%, 20%) and in presence of water vapor (12%). The adsorption curve of FA- Li<sub>4</sub>SiO<sub>4</sub>_0.6 at different temperatures was simulated with the Jander-Zhang model to explore the influence of carbon dioxide diffusion on adsorption reaction. Further experiments showed that the adsorbent had a good sorption capacity in a lower partial pressure of CO<sub>2</sub> and the presence of steam enhanced the mobility of Li<sup>+</sup>. What’s more, FA-Li<sub>4</sub>SiO<sub>4</sub>_0.6, CFA-Li<sub>4</sub>SiO<sub>4</sub>_0.4 and HCl/CFA-Li<sub>4</sub>SiO<sub>4</sub>_0.3 particles showed satisfactory sorption capacity in fixed-bed reactor and excellent cyclic sorption stability during 10 sorption/ desorption cycles.</span></span></span></span>展开更多
基金This work was supported by the Fundamental Research Funds for the Central Universities(2232021A-02 and 2232023Y-01)the National Natural Science Foundation of China(Nos.52122312,22209024 and 22202183).
文摘Electrochemical reduction of CO_(2)into high-value hydrocarbons and alcohols by using Cu-based catalysts is a promising and attractive technology for CO_(2)capture and utilization,resulting from their high catalytic activity and selectivity.The mobility and accessibility of active sites in Cubased catalysts significantly hinder the development of efficient Cu-based catalysts for CO_(2)electrochemical reduction reaction(CO_(2)RR).Herein,a facile and effective strategy is developed to engineer accessible and structural stable Cu sites by incorporating single atomic Cu into the nitrogen cavities of the host graphitic carbon nitride(g-C_(3)N_(4))as the active sites for CO_(2)-to-CH_(4)conversion in CO_(2)RR.By regulating the coordination and density of Cu sites in g-C_(3)N_(4),an optimal catalyst corresponding to a one Cu atom in one nitrogen cavity reaches the highest CH_(4)Faraday efficiency of 49.04%and produces the products with a high CH_(4)/C_(2)H_(4)ratio over 9.This work provides the first experimental study on g-C_(3)N_(4)-supported single Cu atom catalyst for efficient CH_(4)production from CO_(2)RR and suggests a principle in designing highly stable and selective high-efficiency Cu-based catalysts for CO_(2)RR by engineering Cu active sites in 2D materials with porous crystal structures.
基金National Natural Science Foundation of China(12175254,U1832119)National Key R&D Program of China(2021YFE0104800)+2 种基金International Partnership Program of Chinese Academy of Sciences(121631KYSB20200039)International Cooperation Project of Shanghai Science and Technology Commission(20520750200)National Centre for Research and Development(WPC2/1/SCAPOL/2021)。
基金supported by the National Natural Science Foundation of China(No.51972177)the Natural Science Foundation of Ningbo City(No.2021J067)the SJLY2021010 of Ningbo University,Fan 3315 Plan,and Yongjiang Scholar Project.
文摘Localized CdS homojunctions with optimal ratio of high and low index facets are constructed to dy-namically boost H_(2)O splitting into H_(2)energy by hydrothermal method in combination with calcination.By density functional theory,hall effect,and in situ diffuse reflectance infrared Fourier transform spec-troscopy,it is revealed that photo-irradiated e^(−)and h^(+)can be spatially separated and directionally trans-ferred to the reductive high-index facet{002}and oxidative low-index facet{110}of localized CdS homo-junction induced by Fermi level difference of both high and low index facets to dehydrogenate ^(∗)-OH and coupled ^(∗)-O intermediates for H_(2)and O_(2)yield,respectively,along with a solar conversion into hydrogen of 1.93%by AM 1.5 G irradiation at 65℃.The study work suggests a scientific perspective on the optimal ratio of high and low index facets to understand photo-generated charge carrier transfer dynamically and their photocatalytic principle for H_(2)O splitting reaction in kinetics.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.41922023 and 41830425)the Fundamental Research Funds for the Central Universities(Grant Nos.020614380056 and 020614380078).
文摘We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,indicating that Raman quantification of CH4/CO2 molar ratio can be applied to those fluid inclusions(FIs)with high internal pressure(i.e.,>15 MPa).Secondly,the v1(CH4)peak position shifts to lower wavenumber with increasing pressure at constant temperature,confirming that the v1(CH4)peak position can be used to calculate the fluid pressure.However,this method should be carefully calibrated before applying to FI analyses because large discrepancies exist among the reported v1(CH4)-P curves,especially in the highpressure range.These calibrations are applied to CH4-rich FIs in quartz veins of the Silurian Longmaxi black shales in southern Sichuan Basin.The vapor phases of these FIs are mainly composed of CH4 and minor CO2,with CO2 molar fractions from4.4%to 7.4%.The pressure of single-phase gas FI ranges from 103.65 to 128.35 MPa at room temperature,which is higher than previously reported.Thermodynamic calculations supported the presence of extremely high-pressure CH4-saturated fluid(218.03–256.82 MPa at 200°C),which may be responsible for the expulsion of CH4 to adjacent reservoirs.
基金Australian Research Council(Grant No.DP170104017)for the financial support of this projectAT and AS received financial support from the Institute for Catalysis,Hokkaido University as part of their Strategic Research Fellowship grant schemesupported by the Cooperative Research Program of Institute for Catalysis,Hokkaido University(Proposal No.19A1005)。
文摘Dimethoxymethane(DMM),a diesel blend fuel,is being researched with high interest recently due to its unique fuel properties.It is commercially produced via a two step-process of methanol oxidation to make formaldehyde,followed by its condensation with methanol.This study presents a one-pot method of DMM synthesis from methanol mediated carbon dioxide hydrogenation over novel heterogeneous catalysts.The effect of catalyst pore structure was investigated by synthesizing 3 wt%Ru over novel hierarchical zeolite beta(HBEASX)and comparing against Ru doped commercial zeolite beta(CBEA)and desilicated hierarchical zeolite beta(HBZDS).The results showed that 3%Ru/HBEASX provided the best activity for DMM production due to its large average pore size.It also showed the decisive role of SiO_(2)/Al_(2)O_(3)molar ratio,with SiO_(2)/Al_(2)O_(3)=75 providing the highest DMM yield of 13.2 mmol/gcat.LMeOH with ca.100%selectivity.The activity of 3%Ru/HBEAS3 after 5 recycle steps demonstrated the reusability of this catalyst.
基金the National Natural Science Foundation of China through Grant 8206100245the Chinese Meteorological Administration through Grant FY-APP-ZX-2022.0222.
文摘We demonstrate here that global-scale determination of a key ionospheric parameter,the peak height of the F_(2)region(h_(m)F_(2)),can be obtained by making a simple ratio measurement of the atomic oxygen 130.4 and 135.6 nm emissions in the far-ultraviolet nightglow with a nadir-viewing system such as a pair of photometers suitable for flight on a CubeSat.We further demonstrate that measurements from an altitude that is within the typical range of nighttime h_(m)F_(2)250−450 km can provide the ratios that are needed for retrieval of the h_(m)F_(2).Our study is conducted mostly through numerical simulations by using radiative transfer models of the two emissions coupled with empirical models of the atmosphere and ionosphere.Modeling results show that the relationship between the h_(m)F_(2)and the intensity ratio is sensitive to the altitude from which the emissions are observed,primarily because of the distinctly different degrees of resonant scattering of the two emissions in the atmosphere.A roughly quadratic relationship can be established for observations from an orbit of~400 km,which enables h_(m)F_(2)retrieval.Parametric analysis indicates that the relationship can be affected by the ambient atmospheric conditions through resonant scattering and O2 absorption.For typical nighttime conditions with h_(m)F_(2)250−450 km,retrieval of the h_(m)F_(2)from synthetic observations shows that the typical errors are only a few kilometers(up to~20 km),depending on the accuracy of the ambient conditions predicted by the empirical models.Our findings pave the way for use of the 130.4/135.6 nm intensity ratios for global-scale monitoring of the nighttime ionosphere at mid to low latitudes.
文摘It is urgent to develop excellent solid CO<sub>2</sub> sorbents with higher sorption capacity, simpler synthetic process, better thermal stability and lower costs of synthesis in CO<sub>2</sub> capture and storage technologies. In this work, a number of Li<sub>4</sub>SiO<sub>4</sub>-based sorbents synthesized by lithium carbonate with three different kinds of fly ashes in various molar ratios were developed. The results indicate that the Li<sub>2</sub>CO<sub>3</sub>:SiO<sub>2</sub> mole ratio used in the sorbents synthesis significantly affects the CO<sub>2</sub> absorption properties. The sorption capacity increased with the excess of Li<sub>2</sub>CO<sub>3</sub> first and then decreased when the excessive quantity was beyond a certain amount. The experiments found that FA-Li<sub>4</sub>SiO<sub>4</sub>_0.6, CFA-Li<sub>4</sub>SiO<sub>4</sub>_0.4, HCl/CFA-Li<sub>4</sub>SiO<sub>4</sub>_0.3 presented the best sorption ability among these fly ash derived Li<sub><span style="font-family:Verdana;">4</span></sub><span style="font-family:Verdana;">SiO</span><sub><span style="font-family:Verdana;">4</span></sub><span style="font-family:Verdana;"> samples, and the corresponding weight gain was 28.2 wt%, 25.1 wt% and 32.5 wt%, respectively. The three sorbents with the optimal molar ratio were characterized using various morphological </span><span style="font-family:Verdana;">characterization techniques and evaluated by thermogravimetric analysis </span><span style="font-family:Verdana;">for their capacity to chemisorb CO<sub>2</sub> at 450<sup></sup></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;"><span style="font-family:Verdana, Helvetica, Arial;white-space:normal;background-color:#FFFFFF;">°</span></span><span style="font-family:Verdana;"></span><span style="font-family:Verdana;">C</span><span style="font-family:Verdana;"> - 650<sup></sup></span><span style="font-family:Verdana;"><span style="font-family:Verdana, Helvetica, Arial;white-space:normal;background-color:#FFFFFF;">°</span></span><span style="font-family:Verdana;"></span><span style="font-family:Verdana;">C</span><span style="font-family:Verdana;">, diluted CO<sub>2</sub> (10%, 20%) and in presence of water vapor (12%). The adsorption curve of FA- Li<sub>4</sub>SiO<sub>4</sub>_0.6 at different temperatures was simulated with the Jander-Zhang model to explore the influence of carbon dioxide diffusion on adsorption reaction. Further experiments showed that the adsorbent had a good sorption capacity in a lower partial pressure of CO<sub>2</sub> and the presence of steam enhanced the mobility of Li<sup>+</sup>. What’s more, FA-Li<sub>4</sub>SiO<sub>4</sub>_0.6, CFA-Li<sub>4</sub>SiO<sub>4</sub>_0.4 and HCl/CFA-Li<sub>4</sub>SiO<sub>4</sub>_0.3 particles showed satisfactory sorption capacity in fixed-bed reactor and excellent cyclic sorption stability during 10 sorption/ desorption cycles.</span></span></span></span>
