Membrane technology has become the mainstream process for the production of electronic grade hydrogen peroxide(H_(2)O_(2)).But due to the oxidation degradation of the organic membranes(e.g.polyamide)by the strong oxid...Membrane technology has become the mainstream process for the production of electronic grade hydrogen peroxide(H_(2)O_(2)).But due to the oxidation degradation of the organic membranes(e.g.polyamide)by the strong oxidative radicals(e.g.OH)generated via the activation of H_(2)O_(2)by iron ions(Fe^(3+)),the short effective lifetime of membranes remains a challenge.Inorganic nano tin oxide(SnO_(2))has great potential for the removal of Fe^(3+)in strongly oxidative H_(2)O_(2)because of its ability to stabilize H2O_(2)and preferentially adsorb Fe^(3+).Herein,we have designed for the first time a flower-like robust SnO_(2)membrane on the ceramic support by in situ template-free one-step hydrothermal method.The three-dimensional loose pore structure in the membrane built by interlacing SnO_(2)nanosheets endows the SnO_(2)membrane with a high specific surface area and abundant adsorption sites(AOH).Based on the coordination complexation and electrostatic attraction between the SnO_(2)surface and Fe^(3+),the membrane shows a high Fe3+removal efficiency(83%)and permeability(24 L·m^(-2)·h^(-1)·MPa^(-1))in H_(2)O_(2).This study provides an innovative and simple approach to designing robust SnO_(2)membranes for highly efficient removal of Fe^(3+)in harsh environments,such as strong oxidation conditions.展开更多
To expedite the development of industrial technology for producing 2-alkylanthraquinone,a novel pilot test of alkylation-oxidation technology was conducted.The process mainly included anthracene alkylation,separation ...To expedite the development of industrial technology for producing 2-alkylanthraquinone,a novel pilot test of alkylation-oxidation technology was conducted.The process mainly included anthracene alkylation,separation of anthracene and 2-alkylanthracene,oxidation of 2-alkylanthracene,and product purification.Optimal alkylation conditions yielded a 91.1%conversion of anthracene and a 71.73%selectivity for 2-alkylanthracene.To address the separation problem of anthracene and 2-alkylanthracene,solvent-assisted distillation technology was developed,resulting in a 98.9%purity of 2-alkylanthracene and a 91.82%separation yield.When the molar ratio of H2O_(2) to 2-alkylanthracene was 7:1,a 98.96%conversion of 2-alkylanthracene and a 99.94%selectivity for 2-alkylanthraquinone were achieved.A novel composition of 2-alkylanthraquinone,including 2-tert-butylanthraquinone,2-tert-amylanthraquinone,and 2-hexylanthraquinone,was developed.This composition could be effectively separated and purified through a combination of crystallization and washing processes.The elemental composition of the product met the existing standards,and its hydrogenation performance closely matched that of commercially available 2-tert-amylanthraquinone products.展开更多
The mercury species in the ocean(MeHg,Hg^(2+))will be enriched in marine organisms and threaten human health through the food chain.While the excessive H_(2)O_(2)in the metabolic process will produce hydroxyl radicals...The mercury species in the ocean(MeHg,Hg^(2+))will be enriched in marine organisms and threaten human health through the food chain.While the excessive H_(2)O_(2)in the metabolic process will produce hydroxyl radicals and accelerate the aging of human cells,causing a series of diseases.Hence,the cost-effective and rapid detection of mercury and H_(2)O_(2)is of urgent requirement and significance.Here,we synthesized emerging graphitic carbon nitride quantum dots(g-CNQDs)with high fluorescence quantum yield(FLQY)of 42.69%via a bottom-up strategy by a facile one-step hydrothermal method.The g-CNQDs can detect the H_(2)O_(2)and Hg^(2+)through the fluorescence quenching effect between g-CNQDs and detected substances.With the presence of KI,g-CNQDs show concentration-dependent fluorescence toward H_(2)O_(2),with a wide detection range of 1–1000μmolL^(-1)and a low detection limit of 0.23μmolL^(-1).The g-CNQDs also show sensitivity toward Hg^(2+)with a detection range of 0–0.1μmolL^(-1)and a detection limit of 0.038μmolL^(-1).This dual-function detection of g-CNQDs has better practical application capability compared to other quantum dot detection.This study may provide a new strategy for g-CNQDs preparation and construct a fluorescence probe that can be used in various systems involving H_(2)O_(2)and Hg^(2+),providing better support for future bifunctional or multifunction studies.展开更多
This work reports the enhancing effect of a highly cost effective and efficient metal, Fe, incorporation to Co or Ni based Mo/Al_2O_3 catalysts in the oxidative desulfurization(ODS) of dibenzothiophene(DBT) using H_2O...This work reports the enhancing effect of a highly cost effective and efficient metal, Fe, incorporation to Co or Ni based Mo/Al_2O_3 catalysts in the oxidative desulfurization(ODS) of dibenzothiophene(DBT) using H_2O_2 and formic acid as oxidants. The influence of operating parameters i.e. reaction time, catalyst dose, reaction temperature and oxidant amount on oxidation process was investigated. Results revealed that 99% DBT conversion was achieved at 60 °C and 150 min reaction time over Fe–Ni–Mo/Al_2O_3. Fe tremendously enhanced the ODS activity of Co or Ni based Mo/Al_2O_3 catalysts following the activity order: Fe–Ni–Mo/Al_2O_3 NFe–Co–Mo/Al_2O_3 NNi–Mo/Al_2O_3 NCo–Mo/Al_2O_3, while H_2O_2 exhibited higher oxidation activity than formic acid over all catalyst systems. Insight about the surface morphology and textural properties of fresh and spent catalysts were achieved using scanning electron microscopy(SEM), X-ray diffraction(XRD), energy dispersive X-ray(EDX)analysis, Atomic Absorption Spectroscopy(AAS) and BET surface area analysis, which helped in the interpretation of experimental data. The present study can be deemed as an effective approach on industrial level for ODS of fuel oils crediting to its high efficiency, low process/catalyst cost, safety and mild operating condition.展开更多
Two-electron(2 e^(-))oxygen reduction reaction(ORR)shows great promise for on-site electrochemical synthesis of hydrogen peroxide(H_(2)O_(2)).However,it is still a great challenge to design efficient electrocatalysts ...Two-electron(2 e^(-))oxygen reduction reaction(ORR)shows great promise for on-site electrochemical synthesis of hydrogen peroxide(H_(2)O_(2)).However,it is still a great challenge to design efficient electrocatalysts for H_(2)O_(2)synthesis.To address this issue,the logical design of the active site by controlling the geometric and electronic structures is urgently desired.Therefore,using density functional theory(DFT)computations,two kinds of hybrid double-atom supported on C_(2)N nanosheet(RuCu@C_(2)N and PdCu@C_(2)N)are screened out and their H_(2)O_(2)performances are predicted.PdCu@C_(2)N exhibits higher activity for H_(2)O_(2)synthesis with a lower overpotential of 0.12 V than RuCu@C_(2)N(0.59 V),Ru_(3)Cu(110)facet(0.60 V),and PdCu(110)facet(0.54 V).In aqueous phase,the adsorbed O_(2)is further stabilized with bulk H_(2)0 and the thermodynamic rate-determining step of 2 e^(-) ORR change.The activation barrier on PdCu@C_(2)N is 0.43 eV lower than the one on RuCu@C_(2)N with 0.68 eV.PdCu@C_(2)N is near the top of 2 e^(-) ORR volcano plot,and exhibits high selectivity of H_(2)O_(2.)This work provides guidelines for designing highly effective hybrid double-atom electrocatalysts(HDACs)for H_(2)O_(2)synthesis.展开更多
Background:Hepatocellular carcinoma(HCC)has a high incidence and mortality that epitomizes one of the prominent causes of cancer-related death globally.Novel therapeutic approaches are therefore required.Reactive oxyg...Background:Hepatocellular carcinoma(HCC)has a high incidence and mortality that epitomizes one of the prominent causes of cancer-related death globally.Novel therapeutic approaches are therefore required.Reactive oxygen species(ROS)are necessary for maintaining cell cycle.Although ROS is involved in HCC progression,hydrogen peroxide(H2O2)has anti-proliferative effect on HCC.Method:HCC Huh-7 cells were cultured and incubated with various concentrations of H2O2.Paraoxonase activity,levels of malondialdehyde,glutathione and protein oxidation were measured in treated and untreated Huh-7 cells.Furthermore,untreated and treated Huh-7 cells were subjected to two dimensional gel electrophoresis and identified protein spots which were differentially expressed by LC-MS/MS analysis.q RT-PCR was performed to validate the identified proteins.Results:H2O2 depleted glutathione(GSH)with the concomitant up-regulation of GSTP1 and Prx2.H2O2 also increased malondialdehyde and protein oxidation,decreased the activity of paraoxonase in Huh-7 cells.Conclusion:H2O2 could be used as a novel therapeutic agent that might be beneficial in inducing cell cytotoxicity and hence suppress HCC proliferation.展开更多
The degradations of hexazinone and aldicarb by direct ozonation combined an advanced oxidation process( AOP) of O3/H2O2 were investigated in this study focusing on the oxidation mechanism by identifying the hydrogen p...The degradations of hexazinone and aldicarb by direct ozonation combined an advanced oxidation process( AOP) of O3/H2O2 were investigated in this study focusing on the oxidation mechanism by identifying the hydrogen peroxide consumption during the oxidation process of the two chemicals. The results showed that H2O2 could enhance the removal rate of the triazine herbicide hexazinone,and it was consumed along with the variation of removal rate in the light of different pH levels. The addition of H2O2 contributed little to the removal of the thiocarbamate herbicide aldicarb and H2O2 content kept constantly throughout the degradation process. Tert-butyl alcohol( TBA) effectively scavenged the ·OH radical for hexazinone,but had no effect on the removal rate of aldicarb. Aldicarb removal was mainly attributed to direct ozonation molecule in both O3( 97.00%) and O3/H2O2( 96.76%)systems. Moreover,sole O3 could hardly oxidize hexazinone whereas·OH radicals contribute respective 74.70% and 97.50% of removal in O3 system and O3/H2O2 AOP. All of these findings suggest that the mechanism of ·OH radical generation and the chain reaction in O3/H2O2 AOP should be further discussed.展开更多
基金support from the National Key Research and Development Program(2021YFB3801303)the National Natural Science Foundation of China(21838005,21921006)+1 种基金the State Key Laboratory of Materials-Oriented Chemical Engineering(SKL-MCE-22A03)the Key Research and Development Program of Jiangsu Provincial Department of Science and Technology(BE2022033-3).
文摘Membrane technology has become the mainstream process for the production of electronic grade hydrogen peroxide(H_(2)O_(2)).But due to the oxidation degradation of the organic membranes(e.g.polyamide)by the strong oxidative radicals(e.g.OH)generated via the activation of H_(2)O_(2)by iron ions(Fe^(3+)),the short effective lifetime of membranes remains a challenge.Inorganic nano tin oxide(SnO_(2))has great potential for the removal of Fe^(3+)in strongly oxidative H_(2)O_(2)because of its ability to stabilize H2O_(2)and preferentially adsorb Fe^(3+).Herein,we have designed for the first time a flower-like robust SnO_(2)membrane on the ceramic support by in situ template-free one-step hydrothermal method.The three-dimensional loose pore structure in the membrane built by interlacing SnO_(2)nanosheets endows the SnO_(2)membrane with a high specific surface area and abundant adsorption sites(AOH).Based on the coordination complexation and electrostatic attraction between the SnO_(2)surface and Fe^(3+),the membrane shows a high Fe3+removal efficiency(83%)and permeability(24 L·m^(-2)·h^(-1)·MPa^(-1))in H_(2)O_(2).This study provides an innovative and simple approach to designing robust SnO_(2)membranes for highly efficient removal of Fe^(3+)in harsh environments,such as strong oxidation conditions.
基金supported by a grant from the National Natural Science Foundation of China(NSFC 22378437)the SINOPEC Excellent Youth Funds(ST22174).
文摘To expedite the development of industrial technology for producing 2-alkylanthraquinone,a novel pilot test of alkylation-oxidation technology was conducted.The process mainly included anthracene alkylation,separation of anthracene and 2-alkylanthracene,oxidation of 2-alkylanthracene,and product purification.Optimal alkylation conditions yielded a 91.1%conversion of anthracene and a 71.73%selectivity for 2-alkylanthracene.To address the separation problem of anthracene and 2-alkylanthracene,solvent-assisted distillation technology was developed,resulting in a 98.9%purity of 2-alkylanthracene and a 91.82%separation yield.When the molar ratio of H2O_(2) to 2-alkylanthracene was 7:1,a 98.96%conversion of 2-alkylanthracene and a 99.94%selectivity for 2-alkylanthraquinone were achieved.A novel composition of 2-alkylanthraquinone,including 2-tert-butylanthraquinone,2-tert-amylanthraquinone,and 2-hexylanthraquinone,was developed.This composition could be effectively separated and purified through a combination of crystallization and washing processes.The elemental composition of the product met the existing standards,and its hydrogenation performance closely matched that of commercially available 2-tert-amylanthraquinone products.
基金support from the Natural Science Foundation of Shandong Province(No.ZR2021 MB075)National Natural Science Foundation of China(No.51602297)the Opening Fund of State Key Laboratory of High-Efficiency Utilization of Coal and Green Chemical Engineering(No.2021-K53).
文摘The mercury species in the ocean(MeHg,Hg^(2+))will be enriched in marine organisms and threaten human health through the food chain.While the excessive H_(2)O_(2)in the metabolic process will produce hydroxyl radicals and accelerate the aging of human cells,causing a series of diseases.Hence,the cost-effective and rapid detection of mercury and H_(2)O_(2)is of urgent requirement and significance.Here,we synthesized emerging graphitic carbon nitride quantum dots(g-CNQDs)with high fluorescence quantum yield(FLQY)of 42.69%via a bottom-up strategy by a facile one-step hydrothermal method.The g-CNQDs can detect the H_(2)O_(2)and Hg^(2+)through the fluorescence quenching effect between g-CNQDs and detected substances.With the presence of KI,g-CNQDs show concentration-dependent fluorescence toward H_(2)O_(2),with a wide detection range of 1–1000μmolL^(-1)and a low detection limit of 0.23μmolL^(-1).The g-CNQDs also show sensitivity toward Hg^(2+)with a detection range of 0–0.1μmolL^(-1)and a detection limit of 0.038μmolL^(-1).This dual-function detection of g-CNQDs has better practical application capability compared to other quantum dot detection.This study may provide a new strategy for g-CNQDs preparation and construct a fluorescence probe that can be used in various systems involving H_(2)O_(2)and Hg^(2+),providing better support for future bifunctional or multifunction studies.
文摘This work reports the enhancing effect of a highly cost effective and efficient metal, Fe, incorporation to Co or Ni based Mo/Al_2O_3 catalysts in the oxidative desulfurization(ODS) of dibenzothiophene(DBT) using H_2O_2 and formic acid as oxidants. The influence of operating parameters i.e. reaction time, catalyst dose, reaction temperature and oxidant amount on oxidation process was investigated. Results revealed that 99% DBT conversion was achieved at 60 °C and 150 min reaction time over Fe–Ni–Mo/Al_2O_3. Fe tremendously enhanced the ODS activity of Co or Ni based Mo/Al_2O_3 catalysts following the activity order: Fe–Ni–Mo/Al_2O_3 NFe–Co–Mo/Al_2O_3 NNi–Mo/Al_2O_3 NCo–Mo/Al_2O_3, while H_2O_2 exhibited higher oxidation activity than formic acid over all catalyst systems. Insight about the surface morphology and textural properties of fresh and spent catalysts were achieved using scanning electron microscopy(SEM), X-ray diffraction(XRD), energy dispersive X-ray(EDX)analysis, Atomic Absorption Spectroscopy(AAS) and BET surface area analysis, which helped in the interpretation of experimental data. The present study can be deemed as an effective approach on industrial level for ODS of fuel oils crediting to its high efficiency, low process/catalyst cost, safety and mild operating condition.
基金supported by the National Natural Science Foundation of China(Grant No 21625604,21671172,21776251,21706229 and 91934302)。
文摘Two-electron(2 e^(-))oxygen reduction reaction(ORR)shows great promise for on-site electrochemical synthesis of hydrogen peroxide(H_(2)O_(2)).However,it is still a great challenge to design efficient electrocatalysts for H_(2)O_(2)synthesis.To address this issue,the logical design of the active site by controlling the geometric and electronic structures is urgently desired.Therefore,using density functional theory(DFT)computations,two kinds of hybrid double-atom supported on C_(2)N nanosheet(RuCu@C_(2)N and PdCu@C_(2)N)are screened out and their H_(2)O_(2)performances are predicted.PdCu@C_(2)N exhibits higher activity for H_(2)O_(2)synthesis with a lower overpotential of 0.12 V than RuCu@C_(2)N(0.59 V),Ru_(3)Cu(110)facet(0.60 V),and PdCu(110)facet(0.54 V).In aqueous phase,the adsorbed O_(2)is further stabilized with bulk H_(2)0 and the thermodynamic rate-determining step of 2 e^(-) ORR change.The activation barrier on PdCu@C_(2)N is 0.43 eV lower than the one on RuCu@C_(2)N with 0.68 eV.PdCu@C_(2)N is near the top of 2 e^(-) ORR volcano plot,and exhibits high selectivity of H_(2)O_(2.)This work provides guidelines for designing highly effective hybrid double-atom electrocatalysts(HDACs)for H_(2)O_(2)synthesis.
基金supported by a grant from the Higher Education Commission,Islamabad-Pakistan(NRPU 20-4386)。
文摘Background:Hepatocellular carcinoma(HCC)has a high incidence and mortality that epitomizes one of the prominent causes of cancer-related death globally.Novel therapeutic approaches are therefore required.Reactive oxygen species(ROS)are necessary for maintaining cell cycle.Although ROS is involved in HCC progression,hydrogen peroxide(H2O2)has anti-proliferative effect on HCC.Method:HCC Huh-7 cells were cultured and incubated with various concentrations of H2O2.Paraoxonase activity,levels of malondialdehyde,glutathione and protein oxidation were measured in treated and untreated Huh-7 cells.Furthermore,untreated and treated Huh-7 cells were subjected to two dimensional gel electrophoresis and identified protein spots which were differentially expressed by LC-MS/MS analysis.q RT-PCR was performed to validate the identified proteins.Results:H2O2 depleted glutathione(GSH)with the concomitant up-regulation of GSTP1 and Prx2.H2O2 also increased malondialdehyde and protein oxidation,decreased the activity of paraoxonase in Huh-7 cells.Conclusion:H2O2 could be used as a novel therapeutic agent that might be beneficial in inducing cell cytotoxicity and hence suppress HCC proliferation.
基金Science and Technology Project of Shenzhen,China(No.JCYJ20120617141700417)Natural Science Foundation of Guangdong Province,China(No.2012040007855)
文摘The degradations of hexazinone and aldicarb by direct ozonation combined an advanced oxidation process( AOP) of O3/H2O2 were investigated in this study focusing on the oxidation mechanism by identifying the hydrogen peroxide consumption during the oxidation process of the two chemicals. The results showed that H2O2 could enhance the removal rate of the triazine herbicide hexazinone,and it was consumed along with the variation of removal rate in the light of different pH levels. The addition of H2O2 contributed little to the removal of the thiocarbamate herbicide aldicarb and H2O2 content kept constantly throughout the degradation process. Tert-butyl alcohol( TBA) effectively scavenged the ·OH radical for hexazinone,but had no effect on the removal rate of aldicarb. Aldicarb removal was mainly attributed to direct ozonation molecule in both O3( 97.00%) and O3/H2O2( 96.76%)systems. Moreover,sole O3 could hardly oxidize hexazinone whereas·OH radicals contribute respective 74.70% and 97.50% of removal in O3 system and O3/H2O2 AOP. All of these findings suggest that the mechanism of ·OH radical generation and the chain reaction in O3/H2O2 AOP should be further discussed.
文摘为解决2-烷基蒽醌传统生产工艺——苯酐法的污染问题,开发了2-烷基蒽(R-AN)氧化生产2-烷基蒽醌的技术路线。采用过氧化氢盐酸(H_(2)O_(2) /HCl)体系进行R-AN的氧化,通过质谱与核磁共振分析确定主产物为2-烷基蒽醌,副产物为R-AN的一氯和二氯取代物;对氧化反应机理进行研究,明确了氧化反应活性物种为HClO和^(1)O_(2)。系统考察了溶剂种类、反应时间、H_(2)O_(2)及HCl与R-AN的物质的量之比、反应初始液相中的水质量分数[w(H_(2)O)]和R-AN质量浓度[ρ(R-AN)]对氧化反应效果的影响,并基于支持向量回归(SVR)理论建立了收率预测模型。通过模拟优化,确定最佳工艺条件为:常压、70℃、n(H_(2)O_(2))/n(R-AN)=5、n(HCl)n(R-AN)=5、w(H_(2)O)=8%、ρ(R-AN)=0.04 g mL、反应时间8 h。此条件下,所得2-烷基蒽醌的收率大于98%。模型的预测效果好,相对误差大部分在1.5%以内。
