Electrochemical conversion of lignin for the production of high-value heterocyclic aromatic compounds has great potential.We demonstrate the targeted synthesis and cation modulation of NiCo_(2)O_(4)spinel nanoboxes,sy...Electrochemical conversion of lignin for the production of high-value heterocyclic aromatic compounds has great potential.We demonstrate the targeted synthesis and cation modulation of NiCo_(2)O_(4)spinel nanoboxes,synthesized via cation exchange and calcination oxidation.These catalysts exhibit excellent efficacy in the electrocatalytic conversion of lignin model compounds,specifically 2-phenoxy-1-phenylethanol,into nitrogen-containing aromatics,achieving high conversion rates and selectivities.These catalysts were synthesized via a cation exchange and calcination oxidation process,using Prussian blue nanocubes as precursors.The porous architecture and polymetallic composition of the NiCo_(2)O_(4)spinel demonstrated superior performance in electrocatalytic oxidative coupling,achieving a 99.2 wt%conversion rate of the 2-phenoxy-1-phenylethanol with selectivities of 37.5 wt%for quinoline derivatives and 31.5 wt%for phenol.Key innovations include the development of a sustainable one-pot synthesis method for quinoline derivatives,the elucidation of a multistage reaction pathway involving CAO bond cleavage,hydroxyaldol condensation,and CAN bond formation,and a deeper mechanistic understanding derived from DFT simulations.This work establishes a new strategy for lignin valorization,offering a sustainable route to produce high-value nitrogen-containing aromatics from renewable biomass under mild conditions,without the need for additional reagents.展开更多
Supported Pd catalyst is an important noble metal material in recent years due to its high catalytic performance in CO_(2)hydrogenation.A fluidized-bed plasma assisted atomic layer deposition(FP-ALD) process is report...Supported Pd catalyst is an important noble metal material in recent years due to its high catalytic performance in CO_(2)hydrogenation.A fluidized-bed plasma assisted atomic layer deposition(FP-ALD) process is reported to fabricate Pd nanoparticle catalyst over γ-Al_(2)O_(3)or Fe_(2)O_(3)/γ-Al_(2)O_(3)support,using palladium hexafluoroacetylacetonate as the Pd precursor and H_(2)plasma as counter-reactant.Scanning transmission electron microscopy exhibits that highdensity Pd nanoparticles are uniformly dispersed over Fe_(2)O_(3)/γ-Al_(2)O_(3)support with an average diameter of 4.4 nm.The deposited Pd-Fe_(2)O_(3)/γ-Al_(2)O_(3)shows excellent catalytic performance for CO_(2)hydrogenation in a dielectric barrier discharge reactor.Under a typical condition of H_(2)to CO_(2)ratio of 4 in the feed gas,the discharge power of 19.6 W,and gas hourly space velocity of10000 h^(-1),the conversion of CO_(2)is as high as 16.3% with CH_(3)OH and CH4selectivities of 26.5%and 3.9%,respectively.展开更多
Defect engineering of metal-organic frameworks has attracted increasing attention in recent years for potential applications in gas storage and catalysis.In this study,defective UiO-66 is obtained by Ar and H_(2)plasm...Defect engineering of metal-organic frameworks has attracted increasing attention in recent years for potential applications in gas storage and catalysis.In this study,defective UiO-66 is obtained by Ar and H_(2)plasma treatments.Compared with the pristine UiO-66,a new aperture with a size of~4 nm appears for a sample with the plasma modification,indicating the formation of mesopores within UiO-66 framework.Characterization results demonstrate that the pore volume,surface area and the number of Lewis and Br?nsted acid sites can be easily tuned by varying the discharge parameters.The adsorption performance of UiO-66 is evaluated for the adsorption of methyl blue.In comparison to the pristine UiO-66 and the sample with H_(2)plasma treatment,the Ar plasma modified sample shows excellent adsorption activity due to the suitable pore size and volume.Equilibrium adsorption capacity as high as 40.6 mg·g^(-1)is achieved for the UiO-66(Ar)sample.展开更多
A new pulsed chemical vapor deposition（PCVD） process has been developed to fabricate iron（Fe） and iron carbide(Fe1-xCx) thin films at low temperature range from 150 ℃ to 230 ℃.The process employs bis（1,4-di-ter...A new pulsed chemical vapor deposition（PCVD） process has been developed to fabricate iron（Fe） and iron carbide(Fe1-xCx) thin films at low temperature range from 150 ℃ to 230 ℃.The process employs bis（1,4-di-tert-butyl-1,3-diazabutadienyl）iron（Ⅱ） as iron source and hydrogen gas or hydrogen plasma as the coreactant.The films deposited with hydrogen gas are demonstrated polycrystalline with body-centered cubic Fe.However,for the films deposited with hydrogen plasma,the amorphous phase of iron carbide is obtained.The influence of the deposition temperature on iron and iron carbide characteristics have been investigated.展开更多
Single-molecule transistors(SMTs) based on fullerenes and their derivatives have been recognized as a long-sought platform for studying the single-electron transport properties.H_(2)O@C_(60) is a combination of fuller...Single-molecule transistors(SMTs) based on fullerenes and their derivatives have been recognized as a long-sought platform for studying the single-electron transport properties.H_(2)O@C_(60) is a combination of fullerene and H_(2)O,a typical light molecule.Here we use the 'molecular surgery' technique to synthesize the H_(2)O@C_(60) molecule and then construct the H_(2)O@C_(60) SMTs,together with the C_(60) SMTs.Evidences for single-electron transport have been obtained in our measurements,including explicit Coulomb blockade and Coulomb oscillations.We then calculate the detailed parameters of the H_(2)O@C_(60) and C_(60) SMTs using a capacitance model derived from the Coulomb diamond feature,which gives a capacitance ratio of 1:5.05:8.52 for the H_(2)O@C_(60) SMT and 1:29.5:74.8 for the C_(60) SMT.Moreover,the gate efficiency factor a turns out to be 0.0686 in the H_(2)O@C_(60) SMT,about ten times larger than that in the C_(60) SMT.We propose that the enhanced gate efficiency in H_(2)O@C_(60) SMT may be induced by the closer attachment of molecular orbital electron clouds to the gate substrate due to polarization effects of H_(2)O.展开更多
基金National Natural Science Foundation of China (U23A6005 and 22078069)Project funded by China Postdoctoral Science Foundation (GZB20230172 and 2023M740748)。
文摘Electrochemical conversion of lignin for the production of high-value heterocyclic aromatic compounds has great potential.We demonstrate the targeted synthesis and cation modulation of NiCo_(2)O_(4)spinel nanoboxes,synthesized via cation exchange and calcination oxidation.These catalysts exhibit excellent efficacy in the electrocatalytic conversion of lignin model compounds,specifically 2-phenoxy-1-phenylethanol,into nitrogen-containing aromatics,achieving high conversion rates and selectivities.These catalysts were synthesized via a cation exchange and calcination oxidation process,using Prussian blue nanocubes as precursors.The porous architecture and polymetallic composition of the NiCo_(2)O_(4)spinel demonstrated superior performance in electrocatalytic oxidative coupling,achieving a 99.2 wt%conversion rate of the 2-phenoxy-1-phenylethanol with selectivities of 37.5 wt%for quinoline derivatives and 31.5 wt%for phenol.Key innovations include the development of a sustainable one-pot synthesis method for quinoline derivatives,the elucidation of a multistage reaction pathway involving CAO bond cleavage,hydroxyaldol condensation,and CAN bond formation,and a deeper mechanistic understanding derived from DFT simulations.This work establishes a new strategy for lignin valorization,offering a sustainable route to produce high-value nitrogen-containing aromatics from renewable biomass under mild conditions,without the need for additional reagents.
基金financially supported by National Natural Science Foundation of China (Nos. 12075032 and 12105021)Beijing Municipal Natural Science Foundation (Nos.8222055 and 2232061)+1 种基金Yunnan Police College Project (No. YJKF002)Beijing Institute of Graphic Communication Project (No. Ec202207)。
文摘Supported Pd catalyst is an important noble metal material in recent years due to its high catalytic performance in CO_(2)hydrogenation.A fluidized-bed plasma assisted atomic layer deposition(FP-ALD) process is reported to fabricate Pd nanoparticle catalyst over γ-Al_(2)O_(3)or Fe_(2)O_(3)/γ-Al_(2)O_(3)support,using palladium hexafluoroacetylacetonate as the Pd precursor and H_(2)plasma as counter-reactant.Scanning transmission electron microscopy exhibits that highdensity Pd nanoparticles are uniformly dispersed over Fe_(2)O_(3)/γ-Al_(2)O_(3)support with an average diameter of 4.4 nm.The deposited Pd-Fe_(2)O_(3)/γ-Al_(2)O_(3)shows excellent catalytic performance for CO_(2)hydrogenation in a dielectric barrier discharge reactor.Under a typical condition of H_(2)to CO_(2)ratio of 4 in the feed gas,the discharge power of 19.6 W,and gas hourly space velocity of10000 h^(-1),the conversion of CO_(2)is as high as 16.3% with CH_(3)OH and CH4selectivities of 26.5%and 3.9%,respectively.
基金financially supported by National Natural Science Foundation of China(Nos.12075032 and 12105021)the Natural Science Foundation of Beijing Municipality(Nos.KZ202010015022 and 8222055)+1 种基金the Yunnan Police College Project(Nos.YNPC-S2021002 and YJKF002)Beijing Institute of Graphic Communication Project(Nos.Ec202207 and S202210015021)。
文摘Defect engineering of metal-organic frameworks has attracted increasing attention in recent years for potential applications in gas storage and catalysis.In this study,defective UiO-66 is obtained by Ar and H_(2)plasma treatments.Compared with the pristine UiO-66,a new aperture with a size of~4 nm appears for a sample with the plasma modification,indicating the formation of mesopores within UiO-66 framework.Characterization results demonstrate that the pore volume,surface area and the number of Lewis and Br?nsted acid sites can be easily tuned by varying the discharge parameters.The adsorption performance of UiO-66 is evaluated for the adsorption of methyl blue.In comparison to the pristine UiO-66 and the sample with H_(2)plasma treatment,the Ar plasma modified sample shows excellent adsorption activity due to the suitable pore size and volume.Equilibrium adsorption capacity as high as 40.6 mg·g^(-1)is achieved for the UiO-66(Ar)sample.
基金financially supported by National Natural Science Foundation of China(No.11775028)Collaborative Innovation Center of Green Printing&Publishing Technology(No.15208)Beijing Institute of Graphic Communication Project(Nos.Ea201801 04190119001-020 and 12000400001)
文摘A new pulsed chemical vapor deposition（PCVD） process has been developed to fabricate iron（Fe） and iron carbide(Fe1-xCx) thin films at low temperature range from 150 ℃ to 230 ℃.The process employs bis（1,4-di-tert-butyl-1,3-diazabutadienyl）iron（Ⅱ） as iron source and hydrogen gas or hydrogen plasma as the coreactant.The films deposited with hydrogen gas are demonstrated polycrystalline with body-centered cubic Fe.However,for the films deposited with hydrogen plasma,the amorphous phase of iron carbide is obtained.The influence of the deposition temperature on iron and iron carbide characteristics have been investigated.
基金financial support of the National Key R&D Program of China (Grant No. 2022YFA1402)the National Natural Science Foundation of China (Grant Nos. 92161201, T2221003, 12104221, 12104220, 12274208, 12025404, and 12004174)+1 种基金the Natural Science Foundation of Jiangsu Province, China (Grant Nos. BK20200312 and BK20200310)the Fundamental Research Funds for the Central Universities (Grant No. 020414380192)。
文摘Single-molecule transistors(SMTs) based on fullerenes and their derivatives have been recognized as a long-sought platform for studying the single-electron transport properties.H_(2)O@C_(60) is a combination of fullerene and H_(2)O,a typical light molecule.Here we use the 'molecular surgery' technique to synthesize the H_(2)O@C_(60) molecule and then construct the H_(2)O@C_(60) SMTs,together with the C_(60) SMTs.Evidences for single-electron transport have been obtained in our measurements,including explicit Coulomb blockade and Coulomb oscillations.We then calculate the detailed parameters of the H_(2)O@C_(60) and C_(60) SMTs using a capacitance model derived from the Coulomb diamond feature,which gives a capacitance ratio of 1:5.05:8.52 for the H_(2)O@C_(60) SMT and 1:29.5:74.8 for the C_(60) SMT.Moreover,the gate efficiency factor a turns out to be 0.0686 in the H_(2)O@C_(60) SMT,about ten times larger than that in the C_(60) SMT.We propose that the enhanced gate efficiency in H_(2)O@C_(60) SMT may be induced by the closer attachment of molecular orbital electron clouds to the gate substrate due to polarization effects of H_(2)O.
