The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative...The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative solution in a pure acidic system,but the catalyst layer in direct contact with the hydrated proton environment usually leads to H_(2)evolution dominating.Herein,we show that polydimethyldiallyl-ammonium-chloride-coated Ag(Ag@PDDA)electrode exhibits outstanding performance with a FE of 86%,a single-pass conversion of 72%,and a stability of 28 h for CO production in pure-acid MEA compared with ammonium poly(N-methyl-piperidine-co-pterphenyl)decorated Ag(Ag/QAPPT)and cetyltrimethylammonium bromide decorated Ag(Ag/CTAB).The in situ ATR-SEIRAS reveal that PDDA creates a positive charge-rich protective outer layer and an N-rich hybrid inner layer,which not only suppresses the migration of H+during the electrolysis process and blocks the direct contact between H2O and Ag catalyst,but also promotes the generation from CO_(2)to*COOH in a pure-acid system.This work highlights the importance of polyelectrolyte engineering in regulating the electrocatalytic interface and accelerates the development of proton exchange membrane CO_(2)electrolysis.展开更多
Background:Mastitis seriously affects the mammary health of humans and animals.Studies have found that inflammation and oxidative stress play key roles in the occur-rence and development of mastitis.Therefore,in-depth...Background:Mastitis seriously affects the mammary health of humans and animals.Studies have found that inflammation and oxidative stress play key roles in the occur-rence and development of mastitis.Therefore,in-depth research on related molecular mechanisms is of great significance.Methods:Postpartum mice were anesthetized with pentobarbital and administered lipopolysaccharide to develop the mouse mastitis model.Proteomic analysis was per-formed to compare protein expression in mitochondria-associated endoplasmic retic-ulum membranes(MAM)from two mouse mammary gland groups.Western blot was used to detect the expression of MAM-related proteins in mitochondria.AlphaFold3 was used to predict the molecular structures of phosphofurin acidic cluster sorting protein 2(PACS2)and mitofusin 2(MFN2)and their interaction levels.The MFN2-PACS2 interaction was investigated using co-immunoprecipitation and small interfer-ing RNA.Results:The results showed that the inflammation level in the mammary gland tissue of mice with mastitis significantly increased,the total antioxidant capacity decreased,and the expression of MAM-related proteins MFN2 and PACS2 was significantly downregulated.In cell experiments,overexpression of MFN2 can inhibit inflamma-tion and oxidative stress responses,and promote the interaction between MFN2 and PACS2 to affect the formation of MAMs.Conclusion:In summary,this study suggests that mastitis can alter the expression of MAM-related proteins in mouse breast tissue.The interaction between MFN2 and PACS2 regulates the formation of MAMs.Overexpression of MFN2 can promote the formation of MAMs and inhibit inflammation and oxidative stress response in mam-mary epithelial cells.Our results provided a new theoretical basis and potential thera-peutic targets for the prevention and treatment of mastitis.展开更多
Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.展开更多
Pyrrolizidine alkaloids(PAs)and their N-oxides(PANOs)are phytotoxins produced by various plant species and have been emerged as environmental pollutants.The sorption/desorption behaviors of PAs/PANOs in soil are cruci...Pyrrolizidine alkaloids(PAs)and their N-oxides(PANOs)are phytotoxins produced by various plant species and have been emerged as environmental pollutants.The sorption/desorption behaviors of PAs/PANOs in soil are crucial due to the horizontal transfer of these natural products from PA-producing plants to soil and subsequently absorbed by plant roots.This study firstly investigated the sorption/desorption behaviors of PAs/PANOs in tea plantation soils with distinct characteristics.Sorption amounts for seneciphylline(Sp)and seneciphylline-N-oxide(SpNO)in three acidic soils ranged from 2.9 to 5.9μg/g and 1.7 to 2.8μg/g,respectively.Desorption percentages for Sp and SpNO were from 22.2%to 30.5%and 36.1%to 43.9%.In the mixed PAs/PANOs systems,stronger sorption of PAs over PANOs was occurred in tested soils.Additionally,the Freundlich models more precisely described the sorption/desorption isotherms.Cation exchange capacity,sand content and total nitrogen were identified as major influencing factors by linear regression models.Overall,the soils exhibiting higher sorption capacities for compounds with greater hydrophobicity.PANOs were more likely to migrate within soils and be absorbed by tea plants.It contributes to the understanding of environmental fate of PAs/PANOs in tea plantations and provides basic data and clues for the development of PAs/PANOs reduction technology.展开更多
The potential of 2-amino-1-propanol(AP)as a novel depressant in selectively floating ilmenite from titanaugite under weakly acidic conditions was investigated.Micro-flotation results show that AP significantly reduces...The potential of 2-amino-1-propanol(AP)as a novel depressant in selectively floating ilmenite from titanaugite under weakly acidic conditions was investigated.Micro-flotation results show that AP significantly reduces the recovery of titanaugite while having no evident impact on ilmenite flotation.Subsequent bench-scale flotation tests further confirm a remarkable improvement in separation efficiency upon the introduction of AP.Contact angle and adsorption tests reveal a stronger affinity of AP towards the titanaugite surface in comparison to ilmenite.Zeta potential measurements and X-ray photoelectron spectroscopy(XPS)analyses exhibit favorable adsorption characteristics of AP on titanaugite,resulting from a synergy of electrostatic attraction and chemical interaction.In contrast,electrostatic repulsion hinders any significant interaction between AP and the ilmenite surface.These findings highlight the potential of AP as a highly efficient depressant for ilmenite flotation,paving the way for reduced reliance on sulfuric acid in the industry.展开更多
Selective electrocatalysis of two-electron oxygen reduction reaction(2e^(-)ORR)has been recognized as a sustainable and on-site process for hydrogen peroxide(H_(2)O_(2))production.Great progress has been achieved for ...Selective electrocatalysis of two-electron oxygen reduction reaction(2e^(-)ORR)has been recognized as a sustainable and on-site process for hydrogen peroxide(H_(2)O_(2))production.Great progress has been achieved for 2e^(-)ORR in alkaline media.However,it is challenged by insufficient activity and selectiv-ity of the catalysts in acidic electrolytes.Herein,we report sulfur-poisoned PtNi/C catalysts(PtNiSx/C)that could regulate ORR from the 4e^(-)to 2e^(-)pathway.The identified PtNiS0.6/C offers high activity in terms of onset potential of∼0.69 V(vs.RHE)and∼80%selectivity.The mass activity is also compara-ble and outperforms representative Pt-based precious and transition-metal-based catalysts.In addition,it is interestingly found that the Faradaic efficiency further increased to 95%during the long-term elec-trolysis test due to Ni atom surface migration.The electrochemical production of the H_(2)O_(2)system was applied to the electro-Fenton process,which has realized the effective degradation of organic pollutants.This work offers a strategy by sulfur poisoning PtNi/C catalyst to realize Pt-based 2e^(-)ORR active catalysts to electrolysis of H_(2)O_(2)in acidic media.展开更多
Ruthenium dioxide(RuO_(2))is one of the most promising acidic oxygen evolution reaction(OER)catalysts to replace the expensive and prevalent iridium(Ir)-based materials.However,the lattice oxygen oxidation induced Ru ...Ruthenium dioxide(RuO_(2))is one of the most promising acidic oxygen evolution reaction(OER)catalysts to replace the expensive and prevalent iridium(Ir)-based materials.However,the lattice oxygen oxidation induced Ru dissolution during OER compromises the activity and stability.Amorphous materials have been identified as a viable strategy to promote the stability of RuO_(2)in acidic OER applications.This study reported a nanoporous amorphous-rich RuMnO_(x)(A-RuMnO_(x))aerogel for efficient and stable acidic OER.Compared with highly crystalline RuMnO_(x),the weakened Ru–O covalency of A-RuMnO_(x)by forming amorphous structure is favorable to inhibiting the oxidation of lattice oxygen.Meanwhile,this also optimizes the electronic structure of Ru sites from overoxidation and reduces the reaction energy barrier of the rate-determining step.As a result,A-RuMnO_(x)aerogel exhibits an ultra-low overpotential of 145 mV at 10 mA cm^(-2)and durability exceeding 100 h,as well as high mass activity up to 153 mA mg^(-1)_(Ru)at 1.5 V vs.reversible hydrogen electrode(RHE).This work provides valuable guidance for preparing highly active and stable Ru-based catalysts for acidic OER.展开更多
Electrochemical carbon dioxide reduction reaction(CO_(2)RR)converts CO_(2) into valuable chemicals by consuming renewable electricity at mild conditions,making it a promising approach to achieving carbon neutrality.Ho...Electrochemical carbon dioxide reduction reaction(CO_(2)RR)converts CO_(2) into valuable chemicals by consuming renewable electricity at mild conditions,making it a promising approach to achieving carbon neutrality.However,the reaction of CO_(2) with hydroxide ions to form carbonates leads to low carbon utilization and energy efficiency in near-neutral or alkaline CO_(2)RR.The high concentration of protons in acidic media can effectively mitigate carbonate formation and deposition,thereby significantly minimizing carbon loss and energy consumption.Unfortunately,hydrogen evolution reaction(HER)is more kinetically favorable than CO_(2)RR in acidic media.Herein,we comprehensively overview recent progress in acidic CO_(2)RR and propose two strategies derived from the competing reaction pathways of HER and CO_(2)RR:one focuses on regulating the H+mass transport,while the other aims to modulate the intrinsic kinetic activity of CO_(2)RR.The two strategies are designed to compete for the limited active sites on the catalyst surface,inhibit side reactions,and enhance the activity and selectivity of CO_(2)RR.The representative approaches include modulating the interface electric field,constructing a local alkaline environment,and regulating competing adsorption sites.Finally,we also review the technical challenges and future perspectives of acidic CO_(2)RR coupled with membrane electrode assemblies(MEAs).展开更多
Solving the problem of aggregation and nonuniform dispersion of platinum(Pt)nanoparticles(NPs)is the key to obtaining high catalytic activity.Graphene aerogels(GAs)with large accessible specific surface area and abund...Solving the problem of aggregation and nonuniform dispersion of platinum(Pt)nanoparticles(NPs)is the key to obtaining high catalytic activity.Graphene aerogels(GAs)with large accessible specific surface area and abundant surface defects are considered to be excellent substrate materials for reducing Pt agglomeration and enhancing catalytic activity.Herein,Pt-based GA composites(Pt-GA-x)featuring homogeneous particle dispersion and high activity were successfully synthesized through a one-step reduction method.Fourier transform infrared(FTIR),Raman,and X-ray photoelectron spectroscopy(XPS)test results indicate that the presence of a large number of oxygen-containing functionalities in GA for anchoring Pt NPs,and the interaction with GA produces electronically structured Pt and defect-rich GA substrates.The obtained electrocatalyst Pt-GA-2 possesses a large specific surface area(443.46 m^(2)·g^(−1)),low Pt loading(3.08 wt%),and uniformly dispersed Pt NPs(average 42 nm).As an advanced hydrogen evolution reaction(HER)electrocatalyst,an overpotential of 34 mV is achieved at a current density of 10 mA·cm^(−2)in 0.5 M H_(2)SO_(4)electrolyte,together with a low Tafel slope of 33.2 mV·dec^(−1).Hence,high mass activity(5623 mA·mgPt^(−1))and turnover frequency(TOF=2.57 s^(−1)at η=100 mV)can be obtained,which are 6.81 and 6.76 times higher than those of commercial Pt/C catalysts.All these are attributed to enormous surface defects over GA and electron enrichment on Pt NPs.The present study highlights the unique advantages of GA in electrochemical energy conversion and provides new avenues to fabricate advanced HER electrocatalysts.展开更多
BACKGROUND Citrullination is a post-translational modification mediated by calcium-dependent peptidylarginine deiminases that results in notable changes in protein structure and function.Glial fibrillary acidic protei...BACKGROUND Citrullination is a post-translational modification mediated by calcium-dependent peptidylarginine deiminases that results in notable changes in protein structure and function.Glial fibrillary acidic protein(GFAP),which is highly vulnerable to peptidylarginine deiminases-mediated modification,has been found to be elevated in activated hepatic stellate cells,with GFAP-positive hepatic stellate cells and myofibroblasts accumulating within and around areas of hepatic fibrosis.Although recent studies have shown that the expression of citrullinated GFAP(cit-GFAP)increases during hepatic fibrosis,its expression pattern and functional roles in hepatocellular carcinoma(HCC)remain unclear.AIM To determine whether cit-GFAP expression influences the recurrence and survival of patients undergoing hepatic resection for HCC.METHODS We retrospectively analyzed 169 patients with HCC who underwent hepatic resection.Based on the immunohistochemical staining of resected specimens,the enrolled patients were stratified into two groups according to cit-GFAP expression:Low(-/1+)or high(2+/3+)levels of expression.Kaplan-Meier survival curves were constructed to assess overall survival and recurrence-free survival,and comparisons between groups were performed using the log-rank test.RESULTS The median follow-up duration was 33 months(range,1-183).High cit-GFAP expression,identified in 81 patients(48.2%),was significantly associated with male sex,hepatitis B virus positivity,and higher Edmonson-Steiner grade.No associations were found between age,diabetes,hypertension,cirrhosis,Child-Pugh classification,major portal vein invasion,hematological or biochemical parameters,tumor size,or number.Patients exhibiting high cit-GFAP expression demonstrated significantly poorer overall survival.Multivariate Cox analysis identified large tumor size(hazard ratio:2.967;95%confidence interval:1.097-8.024;P=0.032)and high cit-GFAP expression(hazard ratio:2.753;95%confidence interval:1.015-7.464;P=0.047)as independent predictors of poor postoperative survival.Although recurrence rates were high in patients with high cit-GFAP expression,the difference was not statistically significant.CONCLUSION Following curative resection in patients with HCC,high cit-GFAP expression may serve as a potential prognostic biomarker,although further validation through independent cohort studies is warranted.展开更多
The effects of the structure and concentration of impurities on the alkylation of naphthalene with 1-octene catalyzed by chloroaluminate ionic liquid(IL)were investigated.The presence of impurities containing oxygen a...The effects of the structure and concentration of impurities on the alkylation of naphthalene with 1-octene catalyzed by chloroaluminate ionic liquid(IL)were investigated.The presence of impurities containing oxygen and nitrogen led to a decrease in the catalytic performance of chloroaluminate IL.As the water concentration increased to 65 mg·g^(-1),the total selectivity of multi-octylnaphthalene gradually decreased to 42.33%,and the average friction coefficient of the multi-octylnaphthalene base oil gradually increased to 0.201.When the concentration of impurities increased to a critical value,the chloroaluminate IL began to deactivate,leading to a decrease in naphthalene conversion.The critical concentrations for ethanolamine,water,methanol,ether,and diisopentyl sulfide were 33 mg·g^(-1),65 mg·g^(-1),67mg·g^(-1),87 mg·g^(-1),and 123 mg·g^(-1),respectively.Impurities with higher basicity resulted in an earlier onset of chloroaluminate IL deactivation.The changes of Lewis and Brønsted acids in chloroaluminate IL under the influence of impurities were investigated using in situ IR and 27Al NMR spectroscopy.2,6-dimethylpyridine as an indicator could detect the changes of Brønsted acid in chloroaluminate IL better,but the changes of Lewis acid were not obvious because of the overlap between the characteristic peaks.2,6-dichloropyridine as an indicator could exclusively detect the changes of Lewis acid in chloroaluminate IL.With the increase inwater concentration,the Lewis acid in chloroaluminate IL was continuously consumed and converted into Brønsted acid,and the Lewis acid gradually decreased,while the Brønsted acid showed a change of increasing first and then decreasing.展开更多
Hydrogen has emerged as a promising clean energy carrier,and the development of cost-effective electrocatalysts that retain high activity under acidic media is crucial for advancing proton exchange membrane water elec...Hydrogen has emerged as a promising clean energy carrier,and the development of cost-effective electrocatalysts that retain high activity under acidic media is crucial for advancing proton exchange membrane water electrolysis(PEMWE).Here,we propose the SiO_(x)/RuCoO_(x)nanoparticles(SiO_(x)/RuCoO_(x)NPs)as bifunctional electrocatalysts for efficient hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)under acidic media.The Ru-O-Si interface,along with charge transfer between Ru and Co,modulates the d-band electronic structure of the Ru site,achieving superior performance with a low HER overpotential of 18 mV at 10 mA cm^(-2)and a turnover frequency of 8.86 H_(2)s^(-1)at 100 mV.For OER,the overpotential is 217 mV at 10 mA cm^(-2).SiO_(x)/RuCoO_(x)NPs exhibit a cell voltage of 1.482 V at 10 mA cm^(-2)with an energy conversion efficiency of 83.0%.This work takes a significant step toward achieving efficient and cost-effective bifunctional electrocatalysts for water splitting,playing a critical role in the transition to clean energy technologies.展开更多
Cobalt selenide(CoSe_(2))anchored monodisperse Pt presents good acidic 2e^(-)oxygen reduction reaction(ORR)performance;however,conventional preparation methods can only yield ultra-low content of Pt atom catalysts.It ...Cobalt selenide(CoSe_(2))anchored monodisperse Pt presents good acidic 2e^(-)oxygen reduction reaction(ORR)performance;however,conventional preparation methods can only yield ultra-low content of Pt atom catalysts.It is necessary to design catalysts with a high loading of monodisperse Pt to improve the activity and selectivity.Here,we reported anchoring highly reactive Pt atoms by constructing surface Co vacancies on CoSe_(2)(Pt_(1)/md-CoSe_(2)),thereby increasing the co ntent of Pt atoms.The monodisperse Pt is not only a reactive active site but also helps to improve the intrinsic activity of Co around Pt with a suitable electronic structu re,which contributes to the simultaneous enhancement of~*O_(2) adsorption and lowering of the reaction activation energy,accelerating the 2e^(-)ORR kinetics.The Pt_1/md-CoSe_(2) with a 0.2 wt%Pt exhibits high performa nce of electrocatalytic acidic 2e^(-)ORR.The H_(2)O_(2) yield is 1160.2 mmol g_(cat)^(-1).h^(-1)with a Faraday efficiency(FE)of 95.2%(0 V vs.RHE)at 0.1 M HClO_(4),superior to most of the reported literature.Moreover,the catalyst did not deactivate after a stability test of 30 h at the high current density of 100 mA cm^(-2).This work provides guidance for designing catalysts with applications and understanding the action mechanism of monodisperse Pt atoms.展开更多
Graphene encapsulation has been shown to be an effective technique for improving the corrosion resistance of non-noble metal catalysts for the acidic water electrolysis.The key challenge lies in enhancing the electroc...Graphene encapsulation has been shown to be an effective technique for improving the corrosion resistance of non-noble metal catalysts for the acidic water electrolysis.The key challenge lies in enhancing the electrocatalytic activity of graphene-encapsulated metals while maintaining their durability in acidic media.Herein,an electron-transfer-tuning strategy is investigated at the graphene/NiMo interface,aiming to improve the hydrogen evolution reaction(HER)performance of graphene-encapsulated NiMo catalysts.The doping of Ti,a low electronegativity element,into NiMo substrate was confirmed to increase electron transfer from the metal core toward the graphene.The electron-rich state on graphene facilitates the adsorption of positively charged protons on graphene,thereby enabling a Pt/C-comparable performance in 0.5 M H_(2)SO_(4),with only a 3.8%degradation in performance over a 120-h continuous test.The proton exchange membrane(PEM)water electrolyzer assembled by the N-doped grapheneencapsulated Ti-doped NiMo exhibits a smaller cell voltage to achieve a current density of 2.0 A cm^(-2),in comparison to the Pt/C based counterpart.This study proposes a novel electron-transfer-tuning strategy to improve the HER activity of graphene-encapsulated non-noble metal catalysts without sacrificing durability in acidic electrolytes.展开更多
This study explores the adaptation of microbial enzymatic techniques,which were originally developed to eliminate amino impurities in alcoholic beverages,for stabilizing strongly alkaline sodium-based dispersive soils...This study explores the adaptation of microbial enzymatic techniques,which were originally developed to eliminate amino impurities in alcoholic beverages,for stabilizing strongly alkaline sodium-based dispersive soils from check dams.Employing acid urease from Lactobacillus reuteri(L.reuteri)and a control group using soybean-derived urease,this research aimed to modify soil alkalinity through biomineralization.Ultraviolet(UV)mutagenesis optimized L.reuteri strains for biomass and activity.Solution experiments were conducted to assess the effects of pH,temperature,and storage duration on urease activity and to evaluate the calcium carbonate production and crystal morphology of the two ureases under varying calcium ion concentrations.Dispersivity identificationtests and tensile strength evaluations were conducted to analyze the disparities in the modifieddispersive soil treated with the two types of ureases.The results showed that soybean urease should be stored under low-temperature conditions and a neutral pH,whereas acid urease from L.reuteri can be stored at room temperature across a range of pH levels.Both urease treatments effectively reduced soil dispersivity and improved tensile strength significantly(up to 94%and 177%,respectively),with acid urease from L.reuteri resulting in superior soil strengthening and ammonia regulation.These findingssuggest that treating alkaline dispersive soils with acid urease is an efficientand eco-friendly method.展开更多
Proton exchange membrane water electrolyzer(PEMWE)is crucial for the storage and conversion of renewable energy.However,the harsh anode environment and the oxygen evolution reaction(OER),which involves a four-electron...Proton exchange membrane water electrolyzer(PEMWE)is crucial for the storage and conversion of renewable energy.However,the harsh anode environment and the oxygen evolution reaction(OER),which involves a four-electron transfer,result in a significant overpotential that limits the overall efficiency of hydrogen production.Identifying active sites in the OER is crucial for understanding the reaction mechanism and guiding the development of novel electrocatalysts with high activity,cost-effectiveness,and durability.Herein,we summarize the widely accepted OER mechanism in acidic media,in situ characterization and monitoring of active sites during the reaction,and provide a general understanding of the active sites on various catalysts in the OER,including Ir-based metals,Ir-based oxides,carbon/oxide-supported Ir,Ir-based perovskite oxides,and Ir-based pyrochlore oxides.For each type of electrocatalysts,reaction pathways and actual active sites are proposed based on in situ characterization techniques and theoretical calculations.Finally,the challenges and strategic research directions associated with the design of highly efficient Ir-based electrocatalysts are discussed,offering new insights for the further scientific advancement and practical application of acidic OER.展开更多
The increasing level of atmospheric carbon dioxide(CO_(2))caused by intensified human activities has exacerbated the greenhouse effect,calling for the technology of CO_(2)fixation.Among the proposed technologies,elect...The increasing level of atmospheric carbon dioxide(CO_(2))caused by intensified human activities has exacerbated the greenhouse effect,calling for the technology of CO_(2)fixation.Among the proposed technologies,electrocatalytic CO_(2)reduction in acidic electrolytes has garnered significant attention for its potential in sustainable carbon utilization and renewable energy storage.This review provides a summary of recent advancements in acidic CO_(2)reduction,with a focus on catalyst design strategies,the optimization of the local reaction environment,and the effect of cations.We first evaluated the performance and discussed the challenges for acidic CO_(2)reduction in H-type cells,flow cells,and membrane electrode assembly.Afterward,we highlight the innovative strategies for promoting CO_(2)reduction through optimizing the intrinsic activity and regulating the local environment of catalysts.The critical role of cations in enhancing CO_(2)reduction selectivity is also discussed.The review concludes with an outlook on future research directions,especially the need for the design of catalysts and systems that are stable,scalable,and highly efficient.展开更多
The commercialization of polymer electrolyte membrane water splitting technology significantly depends on the oxygen/hydrogen evolution reaction(OER/HER)electrocatalysts;customarily catalyzed by platinum(Pt)and ruthen...The commercialization of polymer electrolyte membrane water splitting technology significantly depends on the oxygen/hydrogen evolution reaction(OER/HER)electrocatalysts;customarily catalyzed by platinum(Pt)and ruthenium/iridium oxides(RuO_(2)/IrO_(2)).In this work,we have devised a novel strategy to improve the catalytic activities towards OER and HER catalysis via the decoration of RuO_(2)with Pt.Pt dopants in ruthenium oxides(Pt-RuO_(2))create more oxygen vacancies inducing a weaker interaction between active site and oxygen reaction intermediates,evidenced by downshifted d band center and increment in e_(g)orbital filling of Ru atom;thereby,the acidic OER performance of Pt-RuO_(2)is enhanced by 3.5-fold than commercial RuO_(2)by mean of turnover frequency at 1.6 V vs.RHE.Moreover,Pt-RuO_(2)exhibits a similar HER performance to commercial Pt/C.The potential for overall water splitting is decreased by 0.18 V at100 mA/cm^(2);besides,an excellent stability is also recorded after the incorporation of Pt dopants.TheΔ_(ε_(d-p))value of Pt-RuO_(2)was 1.76 e V,which is lower than the counterpart of RuO_(2),suggesting easy electron transition between d and p orbitals,suppressing the over-oxidation of RuO_(2);thereby,a higher stability is achieved for Pt-RuO_(2).The invitation of Pt dopants to boost catalytic activity and stability has also been extended to IrO_(2).展开更多
Direct converting carbon dioxide(CO_(2))and propane(C_(3)H_(8))into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO_(2)emission and adequately utilize C_(3)H_(8) in ...Direct converting carbon dioxide(CO_(2))and propane(C_(3)H_(8))into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO_(2)emission and adequately utilize C_(3)H_(8) in shale gas.Owing to their thermodynamic resistance,converting CO_(2)and C_(3)H_(8) respectively remains difficult.Here,we achieve 60.2%aromatics selectivity and 48.8%propane conversion over H-ZSM-5-25 via a zeolite-catalyzing the coupling of CO_(2)and C_(3)H_(8).Operando dual-beam FTIR spectroscopy combined with ^(13)C-labeled CO_(2)tracing experiments revealed that CO_(2)is directly involved in the generation of aromatics,with its carbon atoms selectively embedded into the aromatic ring,bypassing the reverse water-gas shift pathway.Accordingly,a cooperative aromatization mechanism is proposed.Thereinto,lactones,produced from CO_(2)and olefins,are proven to be the key intermediate.This work not only provides an opportunity for simultaneous conversion of CO_(2)and C_(3)H_(8),but also expends coupling strategy designing of CO_(2)and alkanes over acidic zeolites.展开更多
A temperature-sensitive mud cake remover(G315)was developed using ethyl lactate as the primary component.Based on this,a temperature-sensitive acidic completion fluid(CF-G315)was formulated.Core evaluation tests,mud c...A temperature-sensitive mud cake remover(G315)was developed using ethyl lactate as the primary component.Based on this,a temperature-sensitive acidic completion fluid(CF-G315)was formulated.Core evaluation tests,mud cake dissolution tests and corrosion tests were conducted to analyze the mud cake removal performance of G315,the removal efficiency of CF-G315,and its ability to modify the near-wellbore reservoirs,corrosion to casing and hydrolysis performance.Results indicate that ethyl lactate in G315 exhibits weak acidity at room temperature and decomposes into lactic acid under high temperatures.The lactic acid reacts with the calcium carbonate in the mud cake,generating bubbles that dislodge the mud cake and form soluble salts that are subsequently removed by fluid flow,thereby ensuring effective mud cake clearance.CF-G315 removes mud cake efficiently and enhances near-wellbore reservoir permeability.It demonstrates low corrosivity and environmental compatibility,contributing to equipment safety,simplified operational procedures and reduced operational risks.CF-G315 is promising for application in scenarios such as horizontal wells,open-hole completions and gravel pack completions.展开更多
基金financial support of the National Natural Science Foundation of China(NSFC)(52394202,52021004,52301232,and 52476056)the Natural Science Foundation of Chongqing Province(2024NSCQ-MSX1109).
文摘The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative solution in a pure acidic system,but the catalyst layer in direct contact with the hydrated proton environment usually leads to H_(2)evolution dominating.Herein,we show that polydimethyldiallyl-ammonium-chloride-coated Ag(Ag@PDDA)electrode exhibits outstanding performance with a FE of 86%,a single-pass conversion of 72%,and a stability of 28 h for CO production in pure-acid MEA compared with ammonium poly(N-methyl-piperidine-co-pterphenyl)decorated Ag(Ag/QAPPT)and cetyltrimethylammonium bromide decorated Ag(Ag/CTAB).The in situ ATR-SEIRAS reveal that PDDA creates a positive charge-rich protective outer layer and an N-rich hybrid inner layer,which not only suppresses the migration of H+during the electrolysis process and blocks the direct contact between H2O and Ag catalyst,but also promotes the generation from CO_(2)to*COOH in a pure-acid system.This work highlights the importance of polyelectrolyte engineering in regulating the electrocatalytic interface and accelerates the development of proton exchange membrane CO_(2)electrolysis.
基金National Natural Science Foundation of China,Grant/Award Number:32302826 and 32372961Jilin Provincial Special Project for Health Research Talents,Grant/Award Number:2020SCZ40China Postdoctoral Science Foundation,Grant/Award Number:2023M740623。
文摘Background:Mastitis seriously affects the mammary health of humans and animals.Studies have found that inflammation and oxidative stress play key roles in the occur-rence and development of mastitis.Therefore,in-depth research on related molecular mechanisms is of great significance.Methods:Postpartum mice were anesthetized with pentobarbital and administered lipopolysaccharide to develop the mouse mastitis model.Proteomic analysis was per-formed to compare protein expression in mitochondria-associated endoplasmic retic-ulum membranes(MAM)from two mouse mammary gland groups.Western blot was used to detect the expression of MAM-related proteins in mitochondria.AlphaFold3 was used to predict the molecular structures of phosphofurin acidic cluster sorting protein 2(PACS2)and mitofusin 2(MFN2)and their interaction levels.The MFN2-PACS2 interaction was investigated using co-immunoprecipitation and small interfer-ing RNA.Results:The results showed that the inflammation level in the mammary gland tissue of mice with mastitis significantly increased,the total antioxidant capacity decreased,and the expression of MAM-related proteins MFN2 and PACS2 was significantly downregulated.In cell experiments,overexpression of MFN2 can inhibit inflamma-tion and oxidative stress responses,and promote the interaction between MFN2 and PACS2 to affect the formation of MAMs.Conclusion:In summary,this study suggests that mastitis can alter the expression of MAM-related proteins in mouse breast tissue.The interaction between MFN2 and PACS2 regulates the formation of MAMs.Overexpression of MFN2 can promote the formation of MAMs and inhibit inflammation and oxidative stress response in mam-mary epithelial cells.Our results provided a new theoretical basis and potential thera-peutic targets for the prevention and treatment of mastitis.
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
基金supported by the earmarked fund for the Modern Agro-Industry Technology Research System (No.CARS-19)the Innovative Research Team in Chinese Academy of Agricultural Sciences (No.CAAS ASTIP-2014-TRICAAS).
文摘Pyrrolizidine alkaloids(PAs)and their N-oxides(PANOs)are phytotoxins produced by various plant species and have been emerged as environmental pollutants.The sorption/desorption behaviors of PAs/PANOs in soil are crucial due to the horizontal transfer of these natural products from PA-producing plants to soil and subsequently absorbed by plant roots.This study firstly investigated the sorption/desorption behaviors of PAs/PANOs in tea plantation soils with distinct characteristics.Sorption amounts for seneciphylline(Sp)and seneciphylline-N-oxide(SpNO)in three acidic soils ranged from 2.9 to 5.9μg/g and 1.7 to 2.8μg/g,respectively.Desorption percentages for Sp and SpNO were from 22.2%to 30.5%and 36.1%to 43.9%.In the mixed PAs/PANOs systems,stronger sorption of PAs over PANOs was occurred in tested soils.Additionally,the Freundlich models more precisely described the sorption/desorption isotherms.Cation exchange capacity,sand content and total nitrogen were identified as major influencing factors by linear regression models.Overall,the soils exhibiting higher sorption capacities for compounds with greater hydrophobicity.PANOs were more likely to migrate within soils and be absorbed by tea plants.It contributes to the understanding of environmental fate of PAs/PANOs in tea plantations and provides basic data and clues for the development of PAs/PANOs reduction technology.
基金supported by the National Key Research and Development Program of China(No.2019YFC1803501)the National Natural Science Foundation of China(No.52074357)+2 种基金the Natural Science Foundation of Hunan Province,China(No.2022JJ30713)the Vanadium Titanium Union Foundationthe Project of Technology Innovation Center for Comprehensive Utilization of Strategic Mineral Resources,Ministry of Natural Resources,China。
文摘The potential of 2-amino-1-propanol(AP)as a novel depressant in selectively floating ilmenite from titanaugite under weakly acidic conditions was investigated.Micro-flotation results show that AP significantly reduces the recovery of titanaugite while having no evident impact on ilmenite flotation.Subsequent bench-scale flotation tests further confirm a remarkable improvement in separation efficiency upon the introduction of AP.Contact angle and adsorption tests reveal a stronger affinity of AP towards the titanaugite surface in comparison to ilmenite.Zeta potential measurements and X-ray photoelectron spectroscopy(XPS)analyses exhibit favorable adsorption characteristics of AP on titanaugite,resulting from a synergy of electrostatic attraction and chemical interaction.In contrast,electrostatic repulsion hinders any significant interaction between AP and the ilmenite surface.These findings highlight the potential of AP as a highly efficient depressant for ilmenite flotation,paving the way for reduced reliance on sulfuric acid in the industry.
基金financially supported by the National Natu-ral Science Foundation of China(Nos.21805052 and 22227804)the Guangdong Basic and Applied Basic Research Foundation(No.2023B1515020110)+4 种基金the Science and Technology Research Project of Guangzhou(Nos.202102020787 and 2023A03J0030)the De-partment of Science&Technology of Guangdong Province(No.2022A156)the Key Laboratory of Optoelectronic Materials and Sensors in Guangdong Provincial Universities(No.2023KSYS008)the Key Discipline of Materials Science and Engineering,Bureau of Education of Guangzhou(No.20225546)the College Student Innovation and Entrepreneurship Training Program of Guangzhou University(No.XJ202311078029).
文摘Selective electrocatalysis of two-electron oxygen reduction reaction(2e^(-)ORR)has been recognized as a sustainable and on-site process for hydrogen peroxide(H_(2)O_(2))production.Great progress has been achieved for 2e^(-)ORR in alkaline media.However,it is challenged by insufficient activity and selectiv-ity of the catalysts in acidic electrolytes.Herein,we report sulfur-poisoned PtNi/C catalysts(PtNiSx/C)that could regulate ORR from the 4e^(-)to 2e^(-)pathway.The identified PtNiS0.6/C offers high activity in terms of onset potential of∼0.69 V(vs.RHE)and∼80%selectivity.The mass activity is also compara-ble and outperforms representative Pt-based precious and transition-metal-based catalysts.In addition,it is interestingly found that the Faradaic efficiency further increased to 95%during the long-term elec-trolysis test due to Ni atom surface migration.The electrochemical production of the H_(2)O_(2)system was applied to the electro-Fenton process,which has realized the effective degradation of organic pollutants.This work offers a strategy by sulfur poisoning PtNi/C catalyst to realize Pt-based 2e^(-)ORR active catalysts to electrolysis of H_(2)O_(2)in acidic media.
基金financial support from the National Natural Science Foundation of China(22478278,22308246)the Central Government Guides the Local Science and Technology Development Special Fund(YDZJSX20231A015)the Fundamental Research Program of Shanxi Province(202203021212266)。
文摘Ruthenium dioxide(RuO_(2))is one of the most promising acidic oxygen evolution reaction(OER)catalysts to replace the expensive and prevalent iridium(Ir)-based materials.However,the lattice oxygen oxidation induced Ru dissolution during OER compromises the activity and stability.Amorphous materials have been identified as a viable strategy to promote the stability of RuO_(2)in acidic OER applications.This study reported a nanoporous amorphous-rich RuMnO_(x)(A-RuMnO_(x))aerogel for efficient and stable acidic OER.Compared with highly crystalline RuMnO_(x),the weakened Ru–O covalency of A-RuMnO_(x)by forming amorphous structure is favorable to inhibiting the oxidation of lattice oxygen.Meanwhile,this also optimizes the electronic structure of Ru sites from overoxidation and reduces the reaction energy barrier of the rate-determining step.As a result,A-RuMnO_(x)aerogel exhibits an ultra-low overpotential of 145 mV at 10 mA cm^(-2)and durability exceeding 100 h,as well as high mass activity up to 153 mA mg^(-1)_(Ru)at 1.5 V vs.reversible hydrogen electrode(RHE).This work provides valuable guidance for preparing highly active and stable Ru-based catalysts for acidic OER.
基金supported by the National Natural Science Foundation of China(52301259 and 22208019)the Research Fund Program for Young Scholars of Beijing Institute of Technology。
文摘Electrochemical carbon dioxide reduction reaction(CO_(2)RR)converts CO_(2) into valuable chemicals by consuming renewable electricity at mild conditions,making it a promising approach to achieving carbon neutrality.However,the reaction of CO_(2) with hydroxide ions to form carbonates leads to low carbon utilization and energy efficiency in near-neutral or alkaline CO_(2)RR.The high concentration of protons in acidic media can effectively mitigate carbonate formation and deposition,thereby significantly minimizing carbon loss and energy consumption.Unfortunately,hydrogen evolution reaction(HER)is more kinetically favorable than CO_(2)RR in acidic media.Herein,we comprehensively overview recent progress in acidic CO_(2)RR and propose two strategies derived from the competing reaction pathways of HER and CO_(2)RR:one focuses on regulating the H+mass transport,while the other aims to modulate the intrinsic kinetic activity of CO_(2)RR.The two strategies are designed to compete for the limited active sites on the catalyst surface,inhibit side reactions,and enhance the activity and selectivity of CO_(2)RR.The representative approaches include modulating the interface electric field,constructing a local alkaline environment,and regulating competing adsorption sites.Finally,we also review the technical challenges and future perspectives of acidic CO_(2)RR coupled with membrane electrode assemblies(MEAs).
基金supported by the Key Projects of Intergovernmental International Cooperation in the Key R&D programs of the Ministry of Science and Technology of China(No.2021YFE0115800)the National Science Funding Committee of China(No.U20A20250)+1 种基金the Programs of the Science and Technology of Yulin City(No.CXY-2023-ZX04)the funding support from Shccig-Qinling Program.
文摘Solving the problem of aggregation and nonuniform dispersion of platinum(Pt)nanoparticles(NPs)is the key to obtaining high catalytic activity.Graphene aerogels(GAs)with large accessible specific surface area and abundant surface defects are considered to be excellent substrate materials for reducing Pt agglomeration and enhancing catalytic activity.Herein,Pt-based GA composites(Pt-GA-x)featuring homogeneous particle dispersion and high activity were successfully synthesized through a one-step reduction method.Fourier transform infrared(FTIR),Raman,and X-ray photoelectron spectroscopy(XPS)test results indicate that the presence of a large number of oxygen-containing functionalities in GA for anchoring Pt NPs,and the interaction with GA produces electronically structured Pt and defect-rich GA substrates.The obtained electrocatalyst Pt-GA-2 possesses a large specific surface area(443.46 m^(2)·g^(−1)),low Pt loading(3.08 wt%),and uniformly dispersed Pt NPs(average 42 nm).As an advanced hydrogen evolution reaction(HER)electrocatalyst,an overpotential of 34 mV is achieved at a current density of 10 mA·cm^(−2)in 0.5 M H_(2)SO_(4)electrolyte,together with a low Tafel slope of 33.2 mV·dec^(−1).Hence,high mass activity(5623 mA·mgPt^(−1))and turnover frequency(TOF=2.57 s^(−1)at η=100 mV)can be obtained,which are 6.81 and 6.76 times higher than those of commercial Pt/C catalysts.All these are attributed to enormous surface defects over GA and electron enrichment on Pt NPs.The present study highlights the unique advantages of GA in electrochemical energy conversion and provides new avenues to fabricate advanced HER electrocatalysts.
基金Supported by Korean Society of Gastroenterology funded by Korea Research Foundation of Internal Medicine,No.KSG-2022-02.
文摘BACKGROUND Citrullination is a post-translational modification mediated by calcium-dependent peptidylarginine deiminases that results in notable changes in protein structure and function.Glial fibrillary acidic protein(GFAP),which is highly vulnerable to peptidylarginine deiminases-mediated modification,has been found to be elevated in activated hepatic stellate cells,with GFAP-positive hepatic stellate cells and myofibroblasts accumulating within and around areas of hepatic fibrosis.Although recent studies have shown that the expression of citrullinated GFAP(cit-GFAP)increases during hepatic fibrosis,its expression pattern and functional roles in hepatocellular carcinoma(HCC)remain unclear.AIM To determine whether cit-GFAP expression influences the recurrence and survival of patients undergoing hepatic resection for HCC.METHODS We retrospectively analyzed 169 patients with HCC who underwent hepatic resection.Based on the immunohistochemical staining of resected specimens,the enrolled patients were stratified into two groups according to cit-GFAP expression:Low(-/1+)or high(2+/3+)levels of expression.Kaplan-Meier survival curves were constructed to assess overall survival and recurrence-free survival,and comparisons between groups were performed using the log-rank test.RESULTS The median follow-up duration was 33 months(range,1-183).High cit-GFAP expression,identified in 81 patients(48.2%),was significantly associated with male sex,hepatitis B virus positivity,and higher Edmonson-Steiner grade.No associations were found between age,diabetes,hypertension,cirrhosis,Child-Pugh classification,major portal vein invasion,hematological or biochemical parameters,tumor size,or number.Patients exhibiting high cit-GFAP expression demonstrated significantly poorer overall survival.Multivariate Cox analysis identified large tumor size(hazard ratio:2.967;95%confidence interval:1.097-8.024;P=0.032)and high cit-GFAP expression(hazard ratio:2.753;95%confidence interval:1.015-7.464;P=0.047)as independent predictors of poor postoperative survival.Although recurrence rates were high in patients with high cit-GFAP expression,the difference was not statistically significant.CONCLUSION Following curative resection in patients with HCC,high cit-GFAP expression may serve as a potential prognostic biomarker,although further validation through independent cohort studies is warranted.
基金financial support of the Scientific Research Funds of Huaqiao University (605-50Y17073)
文摘The effects of the structure and concentration of impurities on the alkylation of naphthalene with 1-octene catalyzed by chloroaluminate ionic liquid(IL)were investigated.The presence of impurities containing oxygen and nitrogen led to a decrease in the catalytic performance of chloroaluminate IL.As the water concentration increased to 65 mg·g^(-1),the total selectivity of multi-octylnaphthalene gradually decreased to 42.33%,and the average friction coefficient of the multi-octylnaphthalene base oil gradually increased to 0.201.When the concentration of impurities increased to a critical value,the chloroaluminate IL began to deactivate,leading to a decrease in naphthalene conversion.The critical concentrations for ethanolamine,water,methanol,ether,and diisopentyl sulfide were 33 mg·g^(-1),65 mg·g^(-1),67mg·g^(-1),87 mg·g^(-1),and 123 mg·g^(-1),respectively.Impurities with higher basicity resulted in an earlier onset of chloroaluminate IL deactivation.The changes of Lewis and Brønsted acids in chloroaluminate IL under the influence of impurities were investigated using in situ IR and 27Al NMR spectroscopy.2,6-dimethylpyridine as an indicator could detect the changes of Brønsted acid in chloroaluminate IL better,but the changes of Lewis acid were not obvious because of the overlap between the characteristic peaks.2,6-dichloropyridine as an indicator could exclusively detect the changes of Lewis acid in chloroaluminate IL.With the increase inwater concentration,the Lewis acid in chloroaluminate IL was continuously consumed and converted into Brønsted acid,and the Lewis acid gradually decreased,while the Brønsted acid showed a change of increasing first and then decreasing.
基金financially supported by the National Natural Science Foundation of China(No.61921005)the Key R&D Project of Nantong(No.GZ2024004)
文摘Hydrogen has emerged as a promising clean energy carrier,and the development of cost-effective electrocatalysts that retain high activity under acidic media is crucial for advancing proton exchange membrane water electrolysis(PEMWE).Here,we propose the SiO_(x)/RuCoO_(x)nanoparticles(SiO_(x)/RuCoO_(x)NPs)as bifunctional electrocatalysts for efficient hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)under acidic media.The Ru-O-Si interface,along with charge transfer between Ru and Co,modulates the d-band electronic structure of the Ru site,achieving superior performance with a low HER overpotential of 18 mV at 10 mA cm^(-2)and a turnover frequency of 8.86 H_(2)s^(-1)at 100 mV.For OER,the overpotential is 217 mV at 10 mA cm^(-2).SiO_(x)/RuCoO_(x)NPs exhibit a cell voltage of 1.482 V at 10 mA cm^(-2)with an energy conversion efficiency of 83.0%.This work takes a significant step toward achieving efficient and cost-effective bifunctional electrocatalysts for water splitting,playing a critical role in the transition to clean energy technologies.
基金financial support from the National Natural Science Foundation of China(22408196)financial support from the National Natural Science Foundation of China(22379082)+2 种基金the Natural Science Foundation of Shandong(ZR2022QB236)the supported by the State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology(Grant No.MJNYSKL202402)the Taishan Scholars Program(tsqn201909119)。
文摘Cobalt selenide(CoSe_(2))anchored monodisperse Pt presents good acidic 2e^(-)oxygen reduction reaction(ORR)performance;however,conventional preparation methods can only yield ultra-low content of Pt atom catalysts.It is necessary to design catalysts with a high loading of monodisperse Pt to improve the activity and selectivity.Here,we reported anchoring highly reactive Pt atoms by constructing surface Co vacancies on CoSe_(2)(Pt_(1)/md-CoSe_(2)),thereby increasing the co ntent of Pt atoms.The monodisperse Pt is not only a reactive active site but also helps to improve the intrinsic activity of Co around Pt with a suitable electronic structu re,which contributes to the simultaneous enhancement of~*O_(2) adsorption and lowering of the reaction activation energy,accelerating the 2e^(-)ORR kinetics.The Pt_1/md-CoSe_(2) with a 0.2 wt%Pt exhibits high performa nce of electrocatalytic acidic 2e^(-)ORR.The H_(2)O_(2) yield is 1160.2 mmol g_(cat)^(-1).h^(-1)with a Faraday efficiency(FE)of 95.2%(0 V vs.RHE)at 0.1 M HClO_(4),superior to most of the reported literature.Moreover,the catalyst did not deactivate after a stability test of 30 h at the high current density of 100 mA cm^(-2).This work provides guidance for designing catalysts with applications and understanding the action mechanism of monodisperse Pt atoms.
基金supported by the National Natural Science Foundation of China(52302039,52301043)the Guangdong Basic and Applied Basic Research Foundation(2022A1515110676)+2 种基金the Shenzhen Science and Technology Program(JCYJ20220531095404009,RCBS20221008093057027,GXWD20231129113217001)the Postdoctoral Research Startup Expenses of Shenzhen(NA25501001)the Shenzhen Introduce High-Level Talents and Scientific Research Start-up Founds(NA11409005)。
文摘Graphene encapsulation has been shown to be an effective technique for improving the corrosion resistance of non-noble metal catalysts for the acidic water electrolysis.The key challenge lies in enhancing the electrocatalytic activity of graphene-encapsulated metals while maintaining their durability in acidic media.Herein,an electron-transfer-tuning strategy is investigated at the graphene/NiMo interface,aiming to improve the hydrogen evolution reaction(HER)performance of graphene-encapsulated NiMo catalysts.The doping of Ti,a low electronegativity element,into NiMo substrate was confirmed to increase electron transfer from the metal core toward the graphene.The electron-rich state on graphene facilitates the adsorption of positively charged protons on graphene,thereby enabling a Pt/C-comparable performance in 0.5 M H_(2)SO_(4),with only a 3.8%degradation in performance over a 120-h continuous test.The proton exchange membrane(PEM)water electrolyzer assembled by the N-doped grapheneencapsulated Ti-doped NiMo exhibits a smaller cell voltage to achieve a current density of 2.0 A cm^(-2),in comparison to the Pt/C based counterpart.This study proposes a novel electron-transfer-tuning strategy to improve the HER activity of graphene-encapsulated non-noble metal catalysts without sacrificing durability in acidic electrolytes.
基金financiallysupported by the National Natural Science Foundation of China(Grant Nos.52079116,52108343,and 51579215).
文摘This study explores the adaptation of microbial enzymatic techniques,which were originally developed to eliminate amino impurities in alcoholic beverages,for stabilizing strongly alkaline sodium-based dispersive soils from check dams.Employing acid urease from Lactobacillus reuteri(L.reuteri)and a control group using soybean-derived urease,this research aimed to modify soil alkalinity through biomineralization.Ultraviolet(UV)mutagenesis optimized L.reuteri strains for biomass and activity.Solution experiments were conducted to assess the effects of pH,temperature,and storage duration on urease activity and to evaluate the calcium carbonate production and crystal morphology of the two ureases under varying calcium ion concentrations.Dispersivity identificationtests and tensile strength evaluations were conducted to analyze the disparities in the modifieddispersive soil treated with the two types of ureases.The results showed that soybean urease should be stored under low-temperature conditions and a neutral pH,whereas acid urease from L.reuteri can be stored at room temperature across a range of pH levels.Both urease treatments effectively reduced soil dispersivity and improved tensile strength significantly(up to 94%and 177%,respectively),with acid urease from L.reuteri resulting in superior soil strengthening and ammonia regulation.These findingssuggest that treating alkaline dispersive soils with acid urease is an efficientand eco-friendly method.
基金supported by Henan Province Science and Technology Research Project(Grant No.242103810058)Natural Science Foundation of Henan(Grant No.252300421104)+3 种基金National Natural Science Foundation of China(Grant No.52102346)Henan Key Research and Development Project(Grant No.231111230100)Heluo Youth Talent Project(Grant No.2024HLTJ14)Henan Postdoctoral Research Initiation Project(Grant No.HN2022040 and HN2022048).
文摘Proton exchange membrane water electrolyzer(PEMWE)is crucial for the storage and conversion of renewable energy.However,the harsh anode environment and the oxygen evolution reaction(OER),which involves a four-electron transfer,result in a significant overpotential that limits the overall efficiency of hydrogen production.Identifying active sites in the OER is crucial for understanding the reaction mechanism and guiding the development of novel electrocatalysts with high activity,cost-effectiveness,and durability.Herein,we summarize the widely accepted OER mechanism in acidic media,in situ characterization and monitoring of active sites during the reaction,and provide a general understanding of the active sites on various catalysts in the OER,including Ir-based metals,Ir-based oxides,carbon/oxide-supported Ir,Ir-based perovskite oxides,and Ir-based pyrochlore oxides.For each type of electrocatalysts,reaction pathways and actual active sites are proposed based on in situ characterization techniques and theoretical calculations.Finally,the challenges and strategic research directions associated with the design of highly efficient Ir-based electrocatalysts are discussed,offering new insights for the further scientific advancement and practical application of acidic OER.
基金supported by the Young Scientist Funding(22409158,D.R.)from the National Natural Science Foundation of China。
文摘The increasing level of atmospheric carbon dioxide(CO_(2))caused by intensified human activities has exacerbated the greenhouse effect,calling for the technology of CO_(2)fixation.Among the proposed technologies,electrocatalytic CO_(2)reduction in acidic electrolytes has garnered significant attention for its potential in sustainable carbon utilization and renewable energy storage.This review provides a summary of recent advancements in acidic CO_(2)reduction,with a focus on catalyst design strategies,the optimization of the local reaction environment,and the effect of cations.We first evaluated the performance and discussed the challenges for acidic CO_(2)reduction in H-type cells,flow cells,and membrane electrode assembly.Afterward,we highlight the innovative strategies for promoting CO_(2)reduction through optimizing the intrinsic activity and regulating the local environment of catalysts.The critical role of cations in enhancing CO_(2)reduction selectivity is also discussed.The review concludes with an outlook on future research directions,especially the need for the design of catalysts and systems that are stable,scalable,and highly efficient.
基金supported by the National Natural Science Foundation of China(No.22209126)the Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices,Ministry of Education,Jianghan University(No.JDGD-202314)。
文摘The commercialization of polymer electrolyte membrane water splitting technology significantly depends on the oxygen/hydrogen evolution reaction(OER/HER)electrocatalysts;customarily catalyzed by platinum(Pt)and ruthenium/iridium oxides(RuO_(2)/IrO_(2)).In this work,we have devised a novel strategy to improve the catalytic activities towards OER and HER catalysis via the decoration of RuO_(2)with Pt.Pt dopants in ruthenium oxides(Pt-RuO_(2))create more oxygen vacancies inducing a weaker interaction between active site and oxygen reaction intermediates,evidenced by downshifted d band center and increment in e_(g)orbital filling of Ru atom;thereby,the acidic OER performance of Pt-RuO_(2)is enhanced by 3.5-fold than commercial RuO_(2)by mean of turnover frequency at 1.6 V vs.RHE.Moreover,Pt-RuO_(2)exhibits a similar HER performance to commercial Pt/C.The potential for overall water splitting is decreased by 0.18 V at100 mA/cm^(2);besides,an excellent stability is also recorded after the incorporation of Pt dopants.TheΔ_(ε_(d-p))value of Pt-RuO_(2)was 1.76 e V,which is lower than the counterpart of RuO_(2),suggesting easy electron transition between d and p orbitals,suppressing the over-oxidation of RuO_(2);thereby,a higher stability is achieved for Pt-RuO_(2).The invitation of Pt dopants to boost catalytic activity and stability has also been extended to IrO_(2).
文摘Direct converting carbon dioxide(CO_(2))and propane(C_(3)H_(8))into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO_(2)emission and adequately utilize C_(3)H_(8) in shale gas.Owing to their thermodynamic resistance,converting CO_(2)and C_(3)H_(8) respectively remains difficult.Here,we achieve 60.2%aromatics selectivity and 48.8%propane conversion over H-ZSM-5-25 via a zeolite-catalyzing the coupling of CO_(2)and C_(3)H_(8).Operando dual-beam FTIR spectroscopy combined with ^(13)C-labeled CO_(2)tracing experiments revealed that CO_(2)is directly involved in the generation of aromatics,with its carbon atoms selectively embedded into the aromatic ring,bypassing the reverse water-gas shift pathway.Accordingly,a cooperative aromatization mechanism is proposed.Thereinto,lactones,produced from CO_(2)and olefins,are proven to be the key intermediate.This work not only provides an opportunity for simultaneous conversion of CO_(2)and C_(3)H_(8),but also expends coupling strategy designing of CO_(2)and alkanes over acidic zeolites.
基金Supported by National Natural Science Foundation of China(52404010).
文摘A temperature-sensitive mud cake remover(G315)was developed using ethyl lactate as the primary component.Based on this,a temperature-sensitive acidic completion fluid(CF-G315)was formulated.Core evaluation tests,mud cake dissolution tests and corrosion tests were conducted to analyze the mud cake removal performance of G315,the removal efficiency of CF-G315,and its ability to modify the near-wellbore reservoirs,corrosion to casing and hydrolysis performance.Results indicate that ethyl lactate in G315 exhibits weak acidity at room temperature and decomposes into lactic acid under high temperatures.The lactic acid reacts with the calcium carbonate in the mud cake,generating bubbles that dislodge the mud cake and form soluble salts that are subsequently removed by fluid flow,thereby ensuring effective mud cake clearance.CF-G315 removes mud cake efficiently and enhances near-wellbore reservoir permeability.It demonstrates low corrosivity and environmental compatibility,contributing to equipment safety,simplified operational procedures and reduced operational risks.CF-G315 is promising for application in scenarios such as horizontal wells,open-hole completions and gravel pack completions.
