Electrochemical reduction of nitrate,a common pollutant in aquatic environment,to valuable ammonia(NO3-RR) using renewably-sourced electricity has attracted widespread interests,with past efforts mainly focused on des...Electrochemical reduction of nitrate,a common pollutant in aquatic environment,to valuable ammonia(NO3-RR) using renewably-sourced electricity has attracted widespread interests,with past efforts mainly focused on designing electrocatalysts with high activity and selectivity.The detailed correlation between catalyst properties and NO3-RR kinetics,nevertheless,is still not fully understood.In this work,we modulate the surface oxygen species of Cu_(2)O via facet engineering,and systematically study the impact of these oxygen species on the NO_(3)^(-)RR activity.Combining advanced spectroscopic techniques,densi ty fu n ctional theory calculations and molecular dynamics simulations,we find that while oxygen vacancies on Cu_(2)O(111) surface promote the adsorption of reactants and reaction intermediates,hydroxyl groups effectively inhibit the side reaction of hydrogen evolution and facilitate the hydrogenation process of NO3-RR.These two effects work in concert to render Cu_(2)O(111) facet the highest NO3-RR activity relative to those from other facets.Our study provides critical insights into the synergistic effect of exposed facets and surface oxygen species on heterogeneous catalysis,and offers a generalizable,facet engineeringbased strategy for improving the performance of a variety of electrocatalysts important for renewable energy conversion.展开更多
目的观察吸入噻托溴铵粉吸入剂治疗慢性阻塞性肺疾病与阻塞性睡眠呼吸暂停(COPD-OSAHS)重叠综合征患者的肺功能、血气分析的变化,了解其临床意义。方法采用随机对照研究69例COPD-OSAHS重叠综合征患者,将患者分为治疗组(入组44例,完成36...目的观察吸入噻托溴铵粉吸入剂治疗慢性阻塞性肺疾病与阻塞性睡眠呼吸暂停(COPD-OSAHS)重叠综合征患者的肺功能、血气分析的变化,了解其临床意义。方法采用随机对照研究69例COPD-OSAHS重叠综合征患者,将患者分为治疗组(入组44例,完成36例)及对照组(入组39例,完成33例)。治疗组在常规治疗基础上加用噻托溴铵吸入剂(每天1粒,规格:每粒18μg),对照组使用常规治疗。总观察时间12周,观察治疗后患者PaO_2、PaCO_2、FEV1%pre、FEV1/FVC有无差异。结果治疗后治疗组PaO_2(10.05±1.15) k Pa、PaCO_2(5.85±0.90) k Pa、FEV1%pre(52.73±6.72)%、FEV1/FVC(56.52±4.27)%及对照组PaO_2(9.26±1.14) kPa、PaCO_2(5.98±1.00) k Pa、FEV1%pre (48. 12±6. 45)%、FEV1/FVC(54. 29±8.18)%与治疗前比较,差异有统计学意义(P<0.05);比较两组各项指标治疗前后的差值,其差异有统计学意义(P<0.05)。结论吸入噻托溴铵可以改善COPD-OSAHS重叠综合征患者的低氧血症、二氧化碳潴留、高碳酸血症以及肺功能。展开更多
Milliseconds process to produce hydrogen by steam methane reforming (SMR) reaction, based on Ni catalyst rather than noble catalyst such as Pd, Rh or Ru, in micro-channel reactors has been paid more and more attenti...Milliseconds process to produce hydrogen by steam methane reforming (SMR) reaction, based on Ni catalyst rather than noble catalyst such as Pd, Rh or Ru, in micro-channel reactors has been paid more and more attentions in recent years. This work aimed to further improve the catalytic performance of nickel-based catalyst by the introduction of additives, i.e., MgO and FeO, prepared by impregnation method on the micro-channels made of metal-ceramic complex substrate. The prepared catalysts were tested in the same micro-channel reactor by switching the catalyst plates. The results showed that among the tested catalysts Ni-Mg catalyst had the highest activity, especially under harsh conditions, i.e., at high space velocity and/or low reaction temperature. Moreover, the catalyst activity and selectivity were stable during the 12 h on stream test even when the ratio of steam to carbon (SIC) was as low as 1.0. The addition of MgO promoted the active Ni species to have a good dispersion on the substrate, leading to a better catalytic performance for SMR reaction.展开更多
A new photon-in/photon-out endstation at beamline 02B02 of the Shanghai Synchrotron Radiation Facility for studying the electronic structure of energy materials has been constructed and fully opened to users.The endst...A new photon-in/photon-out endstation at beamline 02B02 of the Shanghai Synchrotron Radiation Facility for studying the electronic structure of energy materials has been constructed and fully opened to users.The endstation has the capability to perform soft x-ray absorption spectroscopy in total electron yield and total fluorescence yield modes simultaneously.The photon energy ranges from 40 eV to 2000 eV covering the K-edge of most low Z-elements and the L-edge of 3d transition-metals.The new self-designed channeltron detector allows us to achieve good fluorescence signals at the low photon flux.In addition,we synchronously collect the signals of a standard reference sample and a gold mesh on the upstream to calibrate the photon energy and monitor the beam fluctuation,respectively.In order to cross the pressure gap,in situ gas and liquid cells for soft x-ray absorption spectroscopy are developed to study the samples under realistic working conditions.展开更多
In order to obtain an in-depth insight into the mechanism of charge compensation and capacity fading in LiCoO2, the evolution of electronic structure of LiCoO2 at different cutoff voltages and after different cycles a...In order to obtain an in-depth insight into the mechanism of charge compensation and capacity fading in LiCoO2, the evolution of electronic structure of LiCoO2 at different cutoff voltages and after different cycles are studied by soft x-ray absorption spectroscopy in total electron(TEY) and fluorescence(TFY) detection modes, which provide surface and bulk information, respectively. The spectra of Co L2,3-edge indicate that Co contributes to charge compensation below 4.4 V.Combining with the spectra of O K-edge, it manifests that only O contributes to electron compensation above 4.4 V with the formation of local O 2 p holes both on the surface and in the bulk, where the surficial O evolves more remarkably. The evolution of the O 2 p holes gives an explanation to the origin of O2^-or even O2. A comparison between the TEY and TFY of O K-edge spectra of LiCoO2 cycled in a range from 3 V to 4.6 V indicates both the structural change in the bulk and aggregation of lithium salts on the electrode surface are responsible for the capacity fading. However, the latter is found to play a more important role after many cycles.展开更多
The migration of protons during the oxygen evolution reaction(OER)is a key factor that affects the performance of OER catalysts.To enhance proton transportation,we designed a catalyst based on nickel/iron-pyromellitic...The migration of protons during the oxygen evolution reaction(OER)is a key factor that affects the performance of OER catalysts.To enhance proton transportation,we designed a catalyst based on nickel/iron-pyromellitic acid(NiFe-PMA)prepared by the electrochemical deposition method.This catalyst exhibited a low overpotential of 188 mV at a current density of 10 mA·cm^(-2),a Tafel slope of 28.2 mV·dec^(-1),and long-term stability for 30 days with a current of 50 mA·cm^(-2).We characterized the NiFe-PMA catalyst using various techniques,including Fourier transform infrared(FTIR)spectroscopy,Raman spectroscopy,X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),transmission electron microscopy(TEM),scanning electron microscopy(SEM),and inductively coupled plasma-optical emission spectrometry(ICP-OES).Our results showed that NiFe-PMA contains nickel,iron atoms,and both coordinated and uncoordinated carboxylate groups.Additionally,XPS data confirmed that carboxylate ligands could adjust the outer electronic structure of metal ions,resulting in the high valence state of Ni in NiFe-PMA.The result of XAS indicated that the nickel atoms present in the catalyst might be easier to maintain a higher chemical state.Further investigations using kinetic isotope effects(KIEs)and proton inventory revealed that the uncoordinated carboxylic protons played a crucial role in receiving protons during the OER,which promoted the proton transfer of the rate-determining step of the OER.Our novel electrocatalysts provide a new strategy for designing more active and cost-effective catalysts for the OER.展开更多
The novel contagious primary atypical pneumonia epidemic,which broke out in Wuhan,China,in December 2019,is now formally called Coronavirus Disease 2019(COVID-19),with the causative virus named as Severe Acute Respira...The novel contagious primary atypical pneumonia epidemic,which broke out in Wuhan,China,in December 2019,is now formally called Coronavirus Disease 2019(COVID-19),with the causative virus named as Severe Acute Respiratory Syndrome Coronavirus 2(SARS-CoV-2).1,2 Recent studies have shown that in addition to dyspnea,hypoxemia,and acute respiratory distress,lymphopenia,and cytokine release syndrome are also important clinical features in patients with severe SARS-CoV-2 infection.3 This suggests that homeostasis of the immune system plays an important role in the development of COVID-19 pneumonia.展开更多
Objective:Hepatolenticular degeneration (HLD) is an autosomal recessive disorder that manifests as multiorgan damage due to impaired copper (Cu) metabolism. Female patients with HLD often experience reproductive impai...Objective:Hepatolenticular degeneration (HLD) is an autosomal recessive disorder that manifests as multiorgan damage due to impaired copper (Cu) metabolism. Female patients with HLD often experience reproductive impairments. This study investigated the protective effect of berberine against ovarian damage in toxic-milk (TX) mice, a murine model for HLD.Methods:Mice were categorized into control group, HLD TX group (HLD group), penicillamine (Cu chelator)-treated TX group and berberine-treated TX group. Body weight, ovary weight and the number of ovulated eggs were recorded. Follicular morphology and cellular ultrastructure were examined. Total iron, ferrous iron (Fe2+) and trivalent iron (Fe3+) levels, as well as malondialdehyde (MDA), glutathione(GSH) and oxidized glutathione (GSSG), were measured in the ovaries. Western blot analysis was used to analyze the expression of proteins related to ferroptosis and endoplasmic reticulum (ER) stress.Results:Ovarian tissue damage was evident in the HLD group, with a significant increase in ferroptosis and ER stress compared to the control group. This damage was inhibited by treatment with penicillamine,a Cu chelator. Compared with the HLD group, berberine increased the number of ovulations, and improved ovarian morphology and ultrastructure. Further, we found that berberine reduced total iron,Fe2+, MDA and GSSG levels, elevated GSH levels, decreased the expression of the ferroptosis marker protein prostaglandin-endoperoxide synthase 2 (PTGS2), and increased glutathione peroxidase 4 (GPX4)expression. Furthermore, berberine inhibited the expression of ER stress-associated proteins mediated by the protein kinase RNA-like ER kinase (PERK) pathway.Conclusion:Ferroptosis and ER stress are involved in Cu-induced ovarian damage in TX mice. Berberine ameliorates ovarian damage in HLD TX mice by inhibiting ferroptosis and ER stress.展开更多
基金supported by the Guangdong Provincial Natural Science Foundation,China(2021A1515012330)the National Natural Science Foundation of China(11975102)+2 种基金the State Key Laboratory of Pulp and Paper Engineering(2022PY03)the Guangdong Pearl River Talent Program,China(2017GC010281)supported by ME2 project under contract from the National Natural Science Foundation of China(11227902)。
文摘Electrochemical reduction of nitrate,a common pollutant in aquatic environment,to valuable ammonia(NO3-RR) using renewably-sourced electricity has attracted widespread interests,with past efforts mainly focused on designing electrocatalysts with high activity and selectivity.The detailed correlation between catalyst properties and NO3-RR kinetics,nevertheless,is still not fully understood.In this work,we modulate the surface oxygen species of Cu_(2)O via facet engineering,and systematically study the impact of these oxygen species on the NO_(3)^(-)RR activity.Combining advanced spectroscopic techniques,densi ty fu n ctional theory calculations and molecular dynamics simulations,we find that while oxygen vacancies on Cu_(2)O(111) surface promote the adsorption of reactants and reaction intermediates,hydroxyl groups effectively inhibit the side reaction of hydrogen evolution and facilitate the hydrogenation process of NO3-RR.These two effects work in concert to render Cu_(2)O(111) facet the highest NO3-RR activity relative to those from other facets.Our study provides critical insights into the synergistic effect of exposed facets and surface oxygen species on heterogeneous catalysis,and offers a generalizable,facet engineeringbased strategy for improving the performance of a variety of electrocatalysts important for renewable energy conversion.
文摘目的观察吸入噻托溴铵粉吸入剂治疗慢性阻塞性肺疾病与阻塞性睡眠呼吸暂停(COPD-OSAHS)重叠综合征患者的肺功能、血气分析的变化,了解其临床意义。方法采用随机对照研究69例COPD-OSAHS重叠综合征患者,将患者分为治疗组(入组44例,完成36例)及对照组(入组39例,完成33例)。治疗组在常规治疗基础上加用噻托溴铵吸入剂(每天1粒,规格:每粒18μg),对照组使用常规治疗。总观察时间12周,观察治疗后患者PaO_2、PaCO_2、FEV1%pre、FEV1/FVC有无差异。结果治疗后治疗组PaO_2(10.05±1.15) k Pa、PaCO_2(5.85±0.90) k Pa、FEV1%pre(52.73±6.72)%、FEV1/FVC(56.52±4.27)%及对照组PaO_2(9.26±1.14) kPa、PaCO_2(5.98±1.00) k Pa、FEV1%pre (48. 12±6. 45)%、FEV1/FVC(54. 29±8.18)%与治疗前比较,差异有统计学意义(P<0.05);比较两组各项指标治疗前后的差值,其差异有统计学意义(P<0.05)。结论吸入噻托溴铵可以改善COPD-OSAHS重叠综合征患者的低氧血症、二氧化碳潴留、高碳酸血症以及肺功能。
基金supported by the National Natural Science Foundation of China(No.21176137) and Petro China
文摘Milliseconds process to produce hydrogen by steam methane reforming (SMR) reaction, based on Ni catalyst rather than noble catalyst such as Pd, Rh or Ru, in micro-channel reactors has been paid more and more attentions in recent years. This work aimed to further improve the catalytic performance of nickel-based catalyst by the introduction of additives, i.e., MgO and FeO, prepared by impregnation method on the micro-channels made of metal-ceramic complex substrate. The prepared catalysts were tested in the same micro-channel reactor by switching the catalyst plates. The results showed that among the tested catalysts Ni-Mg catalyst had the highest activity, especially under harsh conditions, i.e., at high space velocity and/or low reaction temperature. Moreover, the catalyst activity and selectivity were stable during the 12 h on stream test even when the ratio of steam to carbon (SIC) was as low as 1.0. The addition of MgO promoted the active Ni species to have a good dispersion on the substrate, leading to a better catalytic performance for SMR reaction.
基金Project supported by the National Natural Science Foundation of China(Grant No.11227902)as part of NSFC ME2 beamline project,Science and Technology Commission of Shanghai Municipality,China(Grant No.14520722100)the National Natural Science Foundation of China(Grant Nos.11905283 and U1632269)
文摘A new photon-in/photon-out endstation at beamline 02B02 of the Shanghai Synchrotron Radiation Facility for studying the electronic structure of energy materials has been constructed and fully opened to users.The endstation has the capability to perform soft x-ray absorption spectroscopy in total electron yield and total fluorescence yield modes simultaneously.The photon energy ranges from 40 eV to 2000 eV covering the K-edge of most low Z-elements and the L-edge of 3d transition-metals.The new self-designed channeltron detector allows us to achieve good fluorescence signals at the low photon flux.In addition,we synchronously collect the signals of a standard reference sample and a gold mesh on the upstream to calibrate the photon energy and monitor the beam fluctuation,respectively.In order to cross the pressure gap,in situ gas and liquid cells for soft x-ray absorption spectroscopy are developed to study the samples under realistic working conditions.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.21503263,U1632269,21473235,and 11227902)
文摘In order to obtain an in-depth insight into the mechanism of charge compensation and capacity fading in LiCoO2, the evolution of electronic structure of LiCoO2 at different cutoff voltages and after different cycles are studied by soft x-ray absorption spectroscopy in total electron(TEY) and fluorescence(TFY) detection modes, which provide surface and bulk information, respectively. The spectra of Co L2,3-edge indicate that Co contributes to charge compensation below 4.4 V.Combining with the spectra of O K-edge, it manifests that only O contributes to electron compensation above 4.4 V with the formation of local O 2 p holes both on the surface and in the bulk, where the surficial O evolves more remarkably. The evolution of the O 2 p holes gives an explanation to the origin of O2^-or even O2. A comparison between the TEY and TFY of O K-edge spectra of LiCoO2 cycled in a range from 3 V to 4.6 V indicates both the structural change in the bulk and aggregation of lithium salts on the electrode surface are responsible for the capacity fading. However, the latter is found to play a more important role after many cycles.
基金supported by the National Key Research and Development Program of Ministry of Science and Technology of China(No.2021YFA1500604)ShanghaiTech University start-up funding.We would like to thank the Analytical Instrumentation Center(#SPST-AIC 10112914)at the School of Physical Science and Technology(SPST)+1 种基金ShanghaiTech University,for their generous support.We are grateful to Peihong Cheng at ShanghaiTech University for assisting with XPS measurements and Siyuan Du for assisting us in the XAS test at Shanghai Synchrotron Radiation Facility(SSRF)We appreciate the Centre for High-Resolution Electron Microscopy(CћEM),which is supported by SPST of ShanghaiTech University under contract No.EM02161943.
文摘The migration of protons during the oxygen evolution reaction(OER)is a key factor that affects the performance of OER catalysts.To enhance proton transportation,we designed a catalyst based on nickel/iron-pyromellitic acid(NiFe-PMA)prepared by the electrochemical deposition method.This catalyst exhibited a low overpotential of 188 mV at a current density of 10 mA·cm^(-2),a Tafel slope of 28.2 mV·dec^(-1),and long-term stability for 30 days with a current of 50 mA·cm^(-2).We characterized the NiFe-PMA catalyst using various techniques,including Fourier transform infrared(FTIR)spectroscopy,Raman spectroscopy,X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),transmission electron microscopy(TEM),scanning electron microscopy(SEM),and inductively coupled plasma-optical emission spectrometry(ICP-OES).Our results showed that NiFe-PMA contains nickel,iron atoms,and both coordinated and uncoordinated carboxylate groups.Additionally,XPS data confirmed that carboxylate ligands could adjust the outer electronic structure of metal ions,resulting in the high valence state of Ni in NiFe-PMA.The result of XAS indicated that the nickel atoms present in the catalyst might be easier to maintain a higher chemical state.Further investigations using kinetic isotope effects(KIEs)and proton inventory revealed that the uncoordinated carboxylic protons played a crucial role in receiving protons during the OER,which promoted the proton transfer of the rate-determining step of the OER.Our novel electrocatalysts provide a new strategy for designing more active and cost-effective catalysts for the OER.
文摘The novel contagious primary atypical pneumonia epidemic,which broke out in Wuhan,China,in December 2019,is now formally called Coronavirus Disease 2019(COVID-19),with the causative virus named as Severe Acute Respiratory Syndrome Coronavirus 2(SARS-CoV-2).1,2 Recent studies have shown that in addition to dyspnea,hypoxemia,and acute respiratory distress,lymphopenia,and cytokine release syndrome are also important clinical features in patients with severe SARS-CoV-2 infection.3 This suggests that homeostasis of the immune system plays an important role in the development of COVID-19 pneumonia.
基金supported by the National Natural Science Foundation of China (No. 82374212, No. 81971446 and No. 81673811)the Clinical Special Translational Project of the Anhui Provincial Science and Technology Department (No. 202204295107020044)the Key Project of the Anhui Provincial Department of Education (No. 2022AH050523)。
文摘Objective:Hepatolenticular degeneration (HLD) is an autosomal recessive disorder that manifests as multiorgan damage due to impaired copper (Cu) metabolism. Female patients with HLD often experience reproductive impairments. This study investigated the protective effect of berberine against ovarian damage in toxic-milk (TX) mice, a murine model for HLD.Methods:Mice were categorized into control group, HLD TX group (HLD group), penicillamine (Cu chelator)-treated TX group and berberine-treated TX group. Body weight, ovary weight and the number of ovulated eggs were recorded. Follicular morphology and cellular ultrastructure were examined. Total iron, ferrous iron (Fe2+) and trivalent iron (Fe3+) levels, as well as malondialdehyde (MDA), glutathione(GSH) and oxidized glutathione (GSSG), were measured in the ovaries. Western blot analysis was used to analyze the expression of proteins related to ferroptosis and endoplasmic reticulum (ER) stress.Results:Ovarian tissue damage was evident in the HLD group, with a significant increase in ferroptosis and ER stress compared to the control group. This damage was inhibited by treatment with penicillamine,a Cu chelator. Compared with the HLD group, berberine increased the number of ovulations, and improved ovarian morphology and ultrastructure. Further, we found that berberine reduced total iron,Fe2+, MDA and GSSG levels, elevated GSH levels, decreased the expression of the ferroptosis marker protein prostaglandin-endoperoxide synthase 2 (PTGS2), and increased glutathione peroxidase 4 (GPX4)expression. Furthermore, berberine inhibited the expression of ER stress-associated proteins mediated by the protein kinase RNA-like ER kinase (PERK) pathway.Conclusion:Ferroptosis and ER stress are involved in Cu-induced ovarian damage in TX mice. Berberine ameliorates ovarian damage in HLD TX mice by inhibiting ferroptosis and ER stress.