为评估晒田期不同水分管理对水稻田温室气体排放影响,2023−2024年在辽宁省沈阳市开展田间试验,在水稻分蘖末期晒田时设置3种水分管理处理,其中,S1处理为晒田期正常灌溉,S2处理为晒田期不灌溉,S3处理为晒田期间隔灌溉。结果表明:①CH_(4...为评估晒田期不同水分管理对水稻田温室气体排放影响,2023−2024年在辽宁省沈阳市开展田间试验,在水稻分蘖末期晒田时设置3种水分管理处理,其中,S1处理为晒田期正常灌溉,S2处理为晒田期不灌溉,S3处理为晒田期间隔灌溉。结果表明:①CH_(4)排放通量呈明显的季节性变化特征,主要集中在分蘖至拔节孕穗期;N_(2)O排放通量则呈现多峰特征,排放高峰多出现在灌浆期。②不同水分管理下CH_(4)和N_(2)O排放通量与土壤理化性质的相关性呈明显差异。S1处理维持强还原环境,增加了CH_(4)排放但抑制N_(2)O排放;S2处理降低了土壤含水量,降低CH_(4)排放的同时增加了N_(2)O排放;S3处理因干湿交替频繁N_(2)O排放通呈现剧烈波动。在2023年S1处理中,CH_(4)排放通量与土壤温度呈显著正相关(P<0.01);S2处理CH_(4)排放通量与土壤孔隙空气相对湿度呈显著正相关(P<0.01),与土壤温度的相关性(P<0.05)次之。S1与S3处理的N_(2)O排放通量均与土壤温度呈显著相关(P均小于0.05),2024年二者相关性发生明显变化,其中S1处理中CH_(4)排放通量与土壤温度相关性减弱,但与pH呈显著负相关(P<0.01)。③不同处理间温室气体综合排放强度(greenhouse gas intensity,GHGI)存在显著差异(P均小于0.05),S2处理的GHGI在2023年与2024年试验中均最低,在维持产量的同时具有减排优势。研究显示,稻田CH_(4)与N_(2)O排放呈此消彼长关系,水分管理为核心调控因素,优化水分调控策略(如精准干湿交替)可实现协同减排。展开更多
The problem of water and sulfur poisoning in flue gas atmosphere remains a significant obstacle for low-temperature deNO_(x) catalysts.This study investigated the sulfation mechanism of the CoMn_(2)O_(4)/CeTiO_(x)(CMC...The problem of water and sulfur poisoning in flue gas atmosphere remains a significant obstacle for low-temperature deNO_(x) catalysts.This study investigated the sulfation mechanism of the CoMn_(2)O_(4)/CeTiO_(x)(CMCT)catalyst during the selective catalytic reduction of NO_(x) with NH3 under conditions containing H2O and SO_(2) at 150℃.Employing a comprehensive suite of time-resolved analysis and characterization techniques,the evolution of sulfate species was systematically categorized into three stages:initial rapid surface sulfate accumulation,the transformation of surface sulfates to bulk metal sulfates,and partial sulfates decomposition after the removal of H2O and SO_(2).These findings indicate that bulk metal sulfates irreversibly deactivate the catalyst by distorting active component lattices and consuming oxygen vacancies,whereas surface sulfates(including ammonium sulfates and surface-coordinated metal sulfates)cause reversible performance loss through decomposition.Furthermore,the competitive adsorption of H2O and SO_(2) significantly influences the catalytic efficiency,with H2O suppressing SO_(2) adsorption while simultaneously enhancing the formation of Brönsted acid sites.This research underscores the critical role of sulfate dynamics on catalyst performance,revealing the enhanced SO_(2) resistance of the Eley-Rideal mechanism facilitated by the Ce-Ti support relative to the Langmuir-Hinshelwood pathway.Collectively,the study unravels the complex interplay of sulfate dynamics influencing catalyst performance and provides potential approaches to mitigate deactivation in demanding atmospheric conditions.展开更多
Peroxymonosulfate(PMS)is commonly used in advanced oxidation processes to degrade organic pollutants in wastewater.In this work,to obtain better PMS activation efficiency,Bi_(4)O_(5)Br_(2)/BCZT(BBT)piezoelectric photo...Peroxymonosulfate(PMS)is commonly used in advanced oxidation processes to degrade organic pollutants in wastewater.In this work,to obtain better PMS activation efficiency,Bi_(4)O_(5)Br_(2)/BCZT(BBT)piezoelectric photocatalyst was designed.Abundant active radicals produced by BBT under visible light irradiation and ultrasonic vibration were used to activate PMS,thereby achieving rapid degradation of high concentration pollutants.With the introduction of BCZT,the catalyst has a strong internal electric field and three-dimensional lamellar structure,which promotes the separation and transfer of electrons and holes.It is worth noting that under optimal reaction conditions,the degradation rate of ARB reached 93%by BBT15 within 10 min.The catalytic experiment combined with the piezoelectric performance test results revealed the key role of piezoelectric photocatalytic reaction in PMS activation.This provides an important prospect for PMS to effectively deal with the degradation of high concentrations of organic pollutants.展开更多
Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Co...Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.展开更多
To construct high-performance aqueous ammonium-ion full batteries,(NH_(4))_(2)V_(6)O_(16)·1.5H_(2)O(NVO)nanoribbon cathodes were prepared by pH-regulated hydrothermal synthesis.Anodes were prepared by growing the...To construct high-performance aqueous ammonium-ion full batteries,(NH_(4))_(2)V_(6)O_(16)·1.5H_(2)O(NVO)nanoribbon cathodes were prepared by pH-regulated hydrothermal synthesis.Anodes were prepared by growing the active material polyaniline(PANI)on carbon cloth.The assembled NVO//PANI full cells exhibit a reversible capacity of 109.5 mA·h/g at a current density of 1.0 A/g and a high energy density of 23 W·h/kg.The ammonium-ion intercalation/extraction mechanism is primarily governed by the pseudocapacitance behavior.These results indicate that NVO is a potential candidate as a cathode material for aqueous ammonium-ion batteries.展开更多
Background:Terpinen-4-ol(T4O),a key constituent of tea tree essential oil and various aromatic plants,has shown promising antiproliferative and pro-apoptotic effects in melanoma and other cancer types.However,its effi...Background:Terpinen-4-ol(T4O),a key constituent of tea tree essential oil and various aromatic plants,has shown promising antiproliferative and pro-apoptotic effects in melanoma and other cancer types.However,its efficacy against cutaneous squamous cell carcinoma(cSCC)remains unclear.Thus,in this study,we investigated the in vivo and in vitro effects of T4O on cSCC cell lines and preliminarily explored its impacting pathways.Methods:Using CCK8 and assay colony formation,we assessed the viability of cSCC A431,SCL-1,and COLO-16 cells treated with T40 at varying concentrations(0,1,2,and 4μM).Flow cytometry was employed to evaluate T4O’s effect on cSCC cell’s cycle progression and apoptosis induction.Additionally,western blotting was utilized to examine the expression intensities of N-cadherin and E-cadherin,two indicative markers of the epithelial-mesenchymal transition(EMT)pathway.T4O’s in vivo effect on inhibiting tumor progression was evaluated on an established xenograft tumor model.Then,the molecular mechanisms of T4O’s antitumor effect were explored by an integrated genome-wide transcriptomics and proteomics study on cSCC A431c cells.Finally,calpain-2’s potential mediator role in T4O’s anti-tumor mechanism was investigated in calpain-2 knockdown cell lines prepared via siRNA transfection.Result:It’s demonstrated that T4O treatment inhibited cSCC proliferation,clonogenicity,migration,and invasion while inducing apoptosis and suppressing the EMT pathway.T4O administration also inhibited cSCC tumorigenesis in the xenograft tumor model.RNA-sequencing and iTRAQ analysis detected significant upregulation of calpain-2 expression in T4O-treated cSCC cells.Western blotting confirmed that T4O significantly increased calpain-2 expression and promoted proteolytic cleavage ofβ-catenin and caspase-12,two calpain-2 target proteins.Importantly,siRNA-mediated calpain-2 knockdown relieved T4O’s suppressive effect on cSCC cell proliferation and motility.Mechanistically,T4O upregulates calpain-2 expression and promotes the cleavage ofβ-catenin and caspase-12,with siRNA-mediated calpain-2 knockdown mitigating T4O’s suppressive effects.Conclusion:These findings suggest that T4O’s antitumor activity in cSCC is mediated through the upregulation of calpain-2 expression and subsequent modulation ofβ-catenin and caspase-12.展开更多
文摘为评估晒田期不同水分管理对水稻田温室气体排放影响,2023−2024年在辽宁省沈阳市开展田间试验,在水稻分蘖末期晒田时设置3种水分管理处理,其中,S1处理为晒田期正常灌溉,S2处理为晒田期不灌溉,S3处理为晒田期间隔灌溉。结果表明:①CH_(4)排放通量呈明显的季节性变化特征,主要集中在分蘖至拔节孕穗期;N_(2)O排放通量则呈现多峰特征,排放高峰多出现在灌浆期。②不同水分管理下CH_(4)和N_(2)O排放通量与土壤理化性质的相关性呈明显差异。S1处理维持强还原环境,增加了CH_(4)排放但抑制N_(2)O排放;S2处理降低了土壤含水量,降低CH_(4)排放的同时增加了N_(2)O排放;S3处理因干湿交替频繁N_(2)O排放通呈现剧烈波动。在2023年S1处理中,CH_(4)排放通量与土壤温度呈显著正相关(P<0.01);S2处理CH_(4)排放通量与土壤孔隙空气相对湿度呈显著正相关(P<0.01),与土壤温度的相关性(P<0.05)次之。S1与S3处理的N_(2)O排放通量均与土壤温度呈显著相关(P均小于0.05),2024年二者相关性发生明显变化,其中S1处理中CH_(4)排放通量与土壤温度相关性减弱,但与pH呈显著负相关(P<0.01)。③不同处理间温室气体综合排放强度(greenhouse gas intensity,GHGI)存在显著差异(P均小于0.05),S2处理的GHGI在2023年与2024年试验中均最低,在维持产量的同时具有减排优势。研究显示,稻田CH_(4)与N_(2)O排放呈此消彼长关系,水分管理为核心调控因素,优化水分调控策略(如精准干湿交替)可实现协同减排。
文摘The problem of water and sulfur poisoning in flue gas atmosphere remains a significant obstacle for low-temperature deNO_(x) catalysts.This study investigated the sulfation mechanism of the CoMn_(2)O_(4)/CeTiO_(x)(CMCT)catalyst during the selective catalytic reduction of NO_(x) with NH3 under conditions containing H2O and SO_(2) at 150℃.Employing a comprehensive suite of time-resolved analysis and characterization techniques,the evolution of sulfate species was systematically categorized into three stages:initial rapid surface sulfate accumulation,the transformation of surface sulfates to bulk metal sulfates,and partial sulfates decomposition after the removal of H2O and SO_(2).These findings indicate that bulk metal sulfates irreversibly deactivate the catalyst by distorting active component lattices and consuming oxygen vacancies,whereas surface sulfates(including ammonium sulfates and surface-coordinated metal sulfates)cause reversible performance loss through decomposition.Furthermore,the competitive adsorption of H2O and SO_(2) significantly influences the catalytic efficiency,with H2O suppressing SO_(2) adsorption while simultaneously enhancing the formation of Brönsted acid sites.This research underscores the critical role of sulfate dynamics on catalyst performance,revealing the enhanced SO_(2) resistance of the Eley-Rideal mechanism facilitated by the Ce-Ti support relative to the Langmuir-Hinshelwood pathway.Collectively,the study unravels the complex interplay of sulfate dynamics influencing catalyst performance and provides potential approaches to mitigate deactivation in demanding atmospheric conditions.
基金financially supported by the National Natural Science Foundation of China(No.51302061)Natural Science Foundation of Hebei Province(No.E2020201021 and E2023201019)+4 种基金Industry-University-Research Cooperation Major Projects of Shijiazhuang(No.241130477A)Research Innovation Team of College of Chemistry and Environmental Science of Hebei University(No.hxkytd2102)Industry-University-research Cooperation Project of Colleges and Universities in Hebei Province(No.CXZX2025016)Hebei Province Innovation Capability Enhancement Plan Project(No.22567620H)Bintuan Science and Technology Program(Nos.2020DB002 and 2022DB009)。
文摘Peroxymonosulfate(PMS)is commonly used in advanced oxidation processes to degrade organic pollutants in wastewater.In this work,to obtain better PMS activation efficiency,Bi_(4)O_(5)Br_(2)/BCZT(BBT)piezoelectric photocatalyst was designed.Abundant active radicals produced by BBT under visible light irradiation and ultrasonic vibration were used to activate PMS,thereby achieving rapid degradation of high concentration pollutants.With the introduction of BCZT,the catalyst has a strong internal electric field and three-dimensional lamellar structure,which promotes the separation and transfer of electrons and holes.It is worth noting that under optimal reaction conditions,the degradation rate of ARB reached 93%by BBT15 within 10 min.The catalytic experiment combined with the piezoelectric performance test results revealed the key role of piezoelectric photocatalytic reaction in PMS activation.This provides an important prospect for PMS to effectively deal with the degradation of high concentrations of organic pollutants.
基金supported by the National Natural Science Foundation of China(22302115,22072079)the Fundamental Research Program of Shanxi Province(202303021221056).
文摘Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.
基金supported by the National Natural Science Foundation of China(Nos.52171200,52371211)the Changsha Special Project,China(No.kh2301006)。
文摘To construct high-performance aqueous ammonium-ion full batteries,(NH_(4))_(2)V_(6)O_(16)·1.5H_(2)O(NVO)nanoribbon cathodes were prepared by pH-regulated hydrothermal synthesis.Anodes were prepared by growing the active material polyaniline(PANI)on carbon cloth.The assembled NVO//PANI full cells exhibit a reversible capacity of 109.5 mA·h/g at a current density of 1.0 A/g and a high energy density of 23 W·h/kg.The ammonium-ion intercalation/extraction mechanism is primarily governed by the pseudocapacitance behavior.These results indicate that NVO is a potential candidate as a cathode material for aqueous ammonium-ion batteries.
基金supported by the Basic Research Program of the Guizhou Science Cooperation Foundation Project(Grant Number:ZK[2021]466)Guizhou Provincial Health Commission(Grant Number:gzwkj2022-062).
文摘Background:Terpinen-4-ol(T4O),a key constituent of tea tree essential oil and various aromatic plants,has shown promising antiproliferative and pro-apoptotic effects in melanoma and other cancer types.However,its efficacy against cutaneous squamous cell carcinoma(cSCC)remains unclear.Thus,in this study,we investigated the in vivo and in vitro effects of T4O on cSCC cell lines and preliminarily explored its impacting pathways.Methods:Using CCK8 and assay colony formation,we assessed the viability of cSCC A431,SCL-1,and COLO-16 cells treated with T40 at varying concentrations(0,1,2,and 4μM).Flow cytometry was employed to evaluate T4O’s effect on cSCC cell’s cycle progression and apoptosis induction.Additionally,western blotting was utilized to examine the expression intensities of N-cadherin and E-cadherin,two indicative markers of the epithelial-mesenchymal transition(EMT)pathway.T4O’s in vivo effect on inhibiting tumor progression was evaluated on an established xenograft tumor model.Then,the molecular mechanisms of T4O’s antitumor effect were explored by an integrated genome-wide transcriptomics and proteomics study on cSCC A431c cells.Finally,calpain-2’s potential mediator role in T4O’s anti-tumor mechanism was investigated in calpain-2 knockdown cell lines prepared via siRNA transfection.Result:It’s demonstrated that T4O treatment inhibited cSCC proliferation,clonogenicity,migration,and invasion while inducing apoptosis and suppressing the EMT pathway.T4O administration also inhibited cSCC tumorigenesis in the xenograft tumor model.RNA-sequencing and iTRAQ analysis detected significant upregulation of calpain-2 expression in T4O-treated cSCC cells.Western blotting confirmed that T4O significantly increased calpain-2 expression and promoted proteolytic cleavage ofβ-catenin and caspase-12,two calpain-2 target proteins.Importantly,siRNA-mediated calpain-2 knockdown relieved T4O’s suppressive effect on cSCC cell proliferation and motility.Mechanistically,T4O upregulates calpain-2 expression and promotes the cleavage ofβ-catenin and caspase-12,with siRNA-mediated calpain-2 knockdown mitigating T4O’s suppressive effects.Conclusion:These findings suggest that T4O’s antitumor activity in cSCC is mediated through the upregulation of calpain-2 expression and subsequent modulation ofβ-catenin and caspase-12.
