Biomass-derived carbon materials are favored for their abundance and sustainability,and ease of preparation and modification.By surface activation and modification they can have a good electrical conductivity,excellen...Biomass-derived carbon materials are favored for their abundance and sustainability,and ease of preparation and modification.By surface activation and modification they can have a good electrical conductivity,excellent catalytic activity,a remarkable adsorption capacity,and different interfacial physicochemical functionalities.Surface-modified biochars have found wide applications in energy storage,environmental remediation,and catalysis.However,achieving precise and controllable modification of their active sites remains a challenge.Recent advances and future prospects for controlling their surface morphology,defect engineering,and surface coating strategies,with particular attention to their means of fabrication,are reviewed.展开更多
Rationale:This case report describes a couple with recurrent fertilization failure despite undergoing multiple cycles of intracytoplasmic sperm injection(ICSI).The principal clinical concern was suspected oocyte activ...Rationale:This case report describes a couple with recurrent fertilization failure despite undergoing multiple cycles of intracytoplasmic sperm injection(ICSI).The principal clinical concern was suspected oocyte activation deficiency(OAD),in which fertilization is impeded due to the oocyte’s inability to initiate embryogenesis,commonly attributed to inadequate intracellular calcium(Ca^(2+))release following sperm injection.Patient concerns:The couple repeatedly experienced complete or near-complete fertilization failure in previous ICSI cycles,raising suspicion of an underlying oocyte activation defect.Diagnosis:Based on the repeated absence of fertilization post-ICSI and clinical history,a diagnosis of suspected OAD leading to recurrent ICSI fertilization failure was considered.Interventions:Artificial oocyte activation(AOA)using the calcium ionophore A23187 was performed.After ICSI,unfertilized oocytes were exposed to the ionophore to induce Ca^(2+)influx,simulating physiological calcium oscillations essential for oocyte activation.The efficacy of intervention was evaluated through subsequent embryonic development,morphological grading,and chromosomal integrity.Outcomes:Following AOA treatment,successful oocyte activation occurred,resulting in the formation of high-grade embryos with normal developmental progression.Chromosomal analysis revealed no detectable abnormalities,indicating genomic stability.Lessons:Calcium ionophore–mediated AOA may serve as an effective adjunct in cases of recurrent ICSI failure attributed to OAD.This case highlights the importance of individualized therapeutic strategies in assisted reproduction;however,further research is needed to refine protocols,validate broader clinical efficacy,and assess long-term safety,including potential epigenetic risks.展开更多
Given that platinum-based drugs are widely used clinically as chemotherapeutic agents,their severe toxic side effects have attracted significant attention.Consequently,the development of novel nanoprodrugs based on lo...Given that platinum-based drugs are widely used clinically as chemotherapeutic agents,their severe toxic side effects have attracted significant attention.Consequently,the development of novel nanoprodrugs based on low-toxicity tetravalent platinum(Pt(Ⅳ))com plexes holds substantial research value.Herein,we discovered that coumarin derivatives exhibit inherent antitumor efficacy and significantly enhance superoxide anion radicals(·O_(2)^(-))generation in aqueous solutions under ultrasound(US)irradiation.Given that·O_(2)^(-)is known to mediate the reduction of Pt(Ⅳ)to divalent platinum(Pt(Ⅱ)),we engineered an US-responsive dual-drug nanoprodrug(P-cisPt(Ⅳ)@5-MOP).This nanoprodrug was prepared by covalently conjugating Pt(Ⅳ)and methoxy polyethylene glycol hydroxyl(m PEG-OH)to a poly(_(L)-glutamic acid)(PLG)carrier,followed by encapsulating coumarin derivatives.Under low-intensity US irradiation(1.5 W/cm^(2),1 MHz,10 min),P-cisPt(Ⅳ)@5-MOP achieved a Pt(Ⅳ)reduction rate of 91.4%.Furthermore,upon US exposure,its half-maximal inhibitory concentration(IC_(50))against 4T1 breast cancer cells decreased dramatically from 25.7μmol/L to 0.1μmol/L.Remarkably,this system combined with US therapy yielded a tumor inhibition rate of 90.9%,with 40%of tumor-bea ring mice achieving com plete eradication of tumors,while exhibiting low systemic toxicity.Collectively,this work not only identifies a novel sonosensitizer capable of generating·O_(2)^(-)but also develops a new class of ultrasound-activatable Pt(Ⅳ)nanoprodrug.展开更多
Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt ...Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt oxyhydroxide @covalent organic frameworks(CoOOH@COFs) S-scheme heterojunction was synthesized,which combined the visible-light-driven photocatalysis and peroxymonosulfate(PMS) activation to synergistically generate abundant reactive oxygen species(ROSs) for TCS degradation.The degradation efficiency of TCS reached 100 % within 8 min in the Vis-CoOOH@COFs/PMS system,and the reaction rate constant was 0.456 min^(-1),which was nearly 1.90 and 2.85 times that of single Co OOH and COFs,and2.36 times that under dark condition,respectively.The density functional theory(DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to Co OOH.Both experimental and theoretical analyses indicated that Co OOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation,enhanced interfacial electron transfer,accelerated PMS activation,and generated multiple ROSs.In particular,photogenerated electrons(e^(-))accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle,while the PMS captured the e-,which significantly decreased the charge combination of Co OOH@COFs.Radicals(O_(2)^(·-),^(·)OH,and SO_(4)^(·-)) and non-radicals(such as ^(1)O_(2),h^(+),and e^(-)) were both presented in the Vis-CoOOH@COFs/PMS system,with O_(2)^(-) playing a dominant role in TCS degradation.Furthermore,the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification.Importantly,the environmentally friendly CoOOH@COFs S-scheme heterojunction exhibited excellent stability and reusability.In conclusion,this study innovatively designed an S-scheme heterojunction in the photocatalytic-PMS activation system,providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.展开更多
The dissolution of iron from the cathode and electrode/electrolyte interface(EEI)during long cycles significantly accelerates the aging process of LiFePO_(4)(LFP)/graphite batteries;there is a lack of systematic under...The dissolution of iron from the cathode and electrode/electrolyte interface(EEI)during long cycles significantly accelerates the aging process of LiFePO_(4)(LFP)/graphite batteries;there is a lack of systematic understanding of the spatial distribution of the EEI interface layer and the dissolve of Fe ions,especially in terms of the mechanism of the cathode-electrolyte interphase(CEI),solid electrolyte interphase(SEI),and iron dissolution.In this study,aged cells were subjected to continuous activation with constant current and multi-step segmented indirect activation(IA)and analyzed for capacity fade,impedance growth,and active Li^(+)mass loss at the EEI and nanoscale levels.The interaction between dissolved Fe^(2+)and the EEI in LFP/graphite pouch batteries was proposed and verified.The findings indicate that during IA process,the electric field facilitates the migration of solvated ions toward the electrodes,while simultaneously inhibiting the formation of organic species such as ROCO_(2)Li.The SEI primarily consists of a mixture of organic and inorganic small molecules,forming a continuous and uniform film on the electrode surface.This study demonstrates that IA favors the formation of a uniform EEI and offers constructive insights for advancing accelerated lifetime prediction strategies in lithium-ion batteries.展开更多
Cells of the central nervous system(CNS)are privileged in lying behind the blood-brain barrier(BBB).Unlike blood vessels in other organs,CNS blood vessels are unique in displaying high electrical resistance and low pe...Cells of the central nervous system(CNS)are privileged in lying behind the blood-brain barrier(BBB).Unlike blood vessels in other organs,CNS blood vessels are unique in displaying high electrical resistance and low permeability.With this unique structure and function,the BBB prevents potentially harmful blood components such as serum proteins,inflammatory cytokines,and inflammatory leukocytes from entering the hallowed space of the CNS and wreaking havoc.In addition to these“tightness”properties,the BBB has an array of specialized transporters designed to import essential nutrients.展开更多
The effect of irreversibly adsorbed Bi on commercial Pt/C catalyst toward glucose electro-oxidation re- action （GOR） in different electrolytes （acidic, neutral, alkaline） is studied. Bi is successfully deposited o...The effect of irreversibly adsorbed Bi on commercial Pt/C catalyst toward glucose electro-oxidation re- action （GOR） in different electrolytes （acidic, neutral, alkaline） is studied. Bi is successfully deposited on Pt/C from Bi3＋ containing acidic solution from 0 to 90% coverage degree. The stability of the Bi layer in acid and alkaline corresponded to previous studies and started to dissolve at 0.7 V and 0.8 V versus re- versible hydrogen electrode （RIIE）, respectively. However, in neutral phosphate buffer the layer showed remarkable stability to at least 1.2V versus RHE. Bi modification at low （20%） and high （80%） coverage showed the highest increase in the activity of Pt/C toward GOR by a factor up to 7 due to the increased poisoning resistance of the modified catalyst. The effect of poisoning was especially reduced at high Bi coverage （80%）, which shows that adsorbate blocked by Bi through the third-body effect is effective. Finally, with or without Bi modification GOR on PtIC was most active in alkaline conditions.展开更多
After being electro-oxidized by cyclic voltammetry(CV) method in 0.5 mol/L H2SO4 solution or in 0.2 mol/L H2O2+0.5 mol/L H2SO4 solution, the Sn/polyaniline (PANI) electrodes were modified with Pt microparticles by pul...After being electro-oxidized by cyclic voltammetry(CV) method in 0.5 mol/L H2SO4 solution or in 0.2 mol/L H2O2+0.5 mol/L H2SO4 solution, the Sn/polyaniline (PANI) electrodes were modified with Pt microparticles by pulse galvanostatic method, thus Pt/Sn hydroxide/PANI electrodes were prepared. The electrocatalytic activities of the Pt/Sn/PANI electrode and Pt/Sn hydroxide/PANI electrode for formaldehyde electro-oxidation were investigated by CV method. The effects of deposition charges (Qdep) of PANI, Sn and Pt, scan rate and formaldehyde concentration on the electrocatalytic activity of Pt/Sn hydroxide/PANI electrode were also studied. The results show that the electrocatalytic activities of the Pt/Sn hydroxide/PANI electrodes are much higher than those of the Pt/Sn/PANI electrode.展开更多
Reproductive hormones associated with the hypothalamic-pituitary-gonadal(HPG)axis are closely linked to bone homeostasis.In this study,we demonstrate that Gonadotropin inhibitory hormone(GnIH,one of the key reproducti...Reproductive hormones associated with the hypothalamic-pituitary-gonadal(HPG)axis are closely linked to bone homeostasis.In this study,we demonstrate that Gonadotropin inhibitory hormone(GnIH,one of the key reproductive hormones upstream of the HPG axis)plays an indispensable role in regulating bone homeostasis and maintaining bone mass.We find that deficiency of GnIH or its receptor Gpr147 leads to a significant reduction in bone mineral density(BMD)in mice primarily by enhancement of osteoclast activation in vivo and in vitro.Mechanistically,GnIH/Gpr147 inhibits osteoclastogenesis by the PI3K/AKT,MAPK,NF-κB and Nfatc1 signaling pathways.Furthermore,GnIH treatment was able to alleviate bone loss in aging,ovariectomy(OVX)or LPS-induced mice.Moreover,the therapy using green light promotes the release of GnIH and rescues OVX-induced bone loss.In humans,serum GnIH increases and bone resorption markers decrease after green light exposure.Therefore,our study elucidates that GnIH plays an important role in maintaining bone homeostasis via modulating osteoclast differentiation and demonstrates the potential of GnIH therapy or green light therapy in preventing osteoporosis.展开更多
To obtain the electrocatalyst with an improved electrocatalytic performance towards formic acid electrooxidation(FAEO), a simple impregnation method is used to prepare Pt3Ni nanoparticles loaded on carbon black, assis...To obtain the electrocatalyst with an improved electrocatalytic performance towards formic acid electrooxidation(FAEO), a simple impregnation method is used to prepare Pt3Ni nanoparticles loaded on carbon black, assisted with electrochemically dealloying process. The X-ray powder diffraction(XRD) results as well as transmission electron microscopy(TEM) analysis of as-synthesized electrocatalyst demonstrates that the reduction temperature has a great influence on the FAEO activity of the dealloyed Pt3Ni nanoparticles. X-ray photoelectron spectroscopy(XPS) analyses confirm the variation in the electronic structure of platinum by incorporation of nickel atoms which reduces chemisorption of toxic carbon monoxide and promotes the dehydrogenation pathway of FAEO. The size of the dealloyed Pt3Ni nanoparticles remains within the range of about 2.7 nm. All electrochemical results illustrate that the performance of the asobtained electrocatalyst towards the FAEO is significantly enhanced. Moreover, the carbon black content,incorporation of Ni atoms, and reduction temperature conditions have been proven to be the key factors for modification of the crystal structure and morphology which leads to enhanced catalytic performance.展开更多
Calcineurin(CN)is a calcium-and calmodulindependent serine/threonine that has been studied in many model organisms including yeast,filamentous fungi,plants,and mammals.Its biological functions range from ion homeostas...Calcineurin(CN)is a calcium-and calmodulindependent serine/threonine that has been studied in many model organisms including yeast,filamentous fungi,plants,and mammals.Its biological functions range from ion homeostasis and virulence in lower eukaryotes to T-cell activation in humans by human nuclear factors of activated T-cells.CN is a heterodimeric protein consisting of a catalytic subunit,calcineurin A(Cna1p),which contains an active site with a dinuclear metal center,and a regulatory Ca^(2+) binding subunit called calcineurin B(Cnb1p)required to activate Cna1p.The calcineurin B subunit has been highly conserved through evolution:For example,the mammalian calcineurin B shows 54%identity with calcineurin B from Saccharomyces cerevisiae.展开更多
The La_(1.7)Pr_(0.3)Mg_(16)Ni hydrogen storage alloy was prepared by medium-frequency induction melting,and then the composite hydrogen storage alloy powder of La_(1.7)Pr_(0.3)Mg_(16)Ni+x wt.%(x=0,2,4,and 6)graphene w...The La_(1.7)Pr_(0.3)Mg_(16)Ni hydrogen storage alloy was prepared by medium-frequency induction melting,and then the composite hydrogen storage alloy powder of La_(1.7)Pr_(0.3)Mg_(16)Ni+x wt.%(x=0,2,4,and 6)graphene was prepared by ball milling for 10 h.The effect of the addition of graphene on the activation and hydrogen de/absorption properties of La_(1.7)Pr_(0.3)Mg_(16)Ni alloy was studied.The result demonstrated that these composite alloys were composed of La_(2)Mg_(17),La_(2)Ni_(3),and Mg_(2)Ni phases.After saturated hydrogen absorption,it was composed of LaH_(3),Mg_(2)NiH_(4),and MgH_(2)phases,while during the dehydrogenation process,it was composed of LaH_(3),Mg,and Mg_(2)Ni phases.The addition of graphene can help get a more homogeneous granule after ball milling and accelerate the first activation of dehydrogenation/hydrogen absorption.The hydrogen release activation energy of the alloys first decreases and then increases as the graphene content increases from x=0 wt.%to x=6 wt.%.The minimum activation energy of the composite hydrogen storage alloy is 51.22 kJ mol^(-1) when x=4 wt.%.展开更多
The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development.This study proposes a technique for synthesizing carbon adsorbents using trace K...The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development.This study proposes a technique for synthesizing carbon adsorbents using trace KOH-catalyzed CO_(2) activation.Comprehensive investigations were conducted on three aspects:physicochemical structure evolution of biochar,mechanistic understanding of trace KOH-facilitated CO_(2) activation processes,and application characteristics for CO_(2) adsorption.Results demonstrate that biochar activated by trace KOH(<10%)and CO_(2) achieves comparable specific surface area(1244.09 m^(2)/g)to that obtained with 100%KOH activation(1425.10 m^(2)/g).The pore structure characteristics(specific surface area and pore volume)are governed by CO and CH4 generated through K-salt catalyzed reactions between CO_(2) and biochar.The optimal CO_(2) adsorption capacities of KBC adsorbent reached 4.70 mmol/g(0℃)and 7.25 mmol/g(25℃),representing the maximum values among comparable carbon adsorbents.The 5%KBC-CO_(2) sample exhibited CO_(2) adsorption capacities of 3.19 and 5.01 mmol/g under respective conditions,attaining current average performance levels.Notably,CO_(2)/N_(2) selectivity(85∶15,volume ratio)reached 64.71 at 0.02 bar with robust cycling stability.Molecular dynamics simulations revealed that oxygen-containing functional groups accelerate CO_(2) adsorption kinetics and enhance micropore storage capacity.This technical route offers simplicity,environmental compatibility,and scalability,providing critical references for large-scale preparation of high-quality carbon materials.展开更多
Lowering the synthesis temperature of boron nitride nanotubes(BNNTs)is crucial for their development.The primary reason for adopting a high temperature is to enable the effective activation of highmelting-point solid ...Lowering the synthesis temperature of boron nitride nanotubes(BNNTs)is crucial for their development.The primary reason for adopting a high temperature is to enable the effective activation of highmelting-point solid boron.In this study,we developed a novel approach for efficiently activating boron by introducing alkali metal compounds into the conventional MgO–B system.This approach can be adopted to form various low-melting-point AM–Mg–B–O growth systems.These growth systems have improved catalytic capability and reactivity even under low-temperature conditions,facilitating the synthesis of BNNTs at temperatures as low as 850℃.In addition,molecular dynamics simulations based on density functional theory theoretically demonstrate that the systems maintain a liquid state at low temperatures and interact with N atoms to form BN chains.These findings offer novel insights into the design of boron activation and are expected to facilitate research on the low-temperature synthesis of BNNTs.展开更多
Itaconate,a macrophage-specific anti-inflammatory metabolite,has recently emerged as a critical regulator in rheumatoid arthritis pathogenesis.We found that itaconate is a TNF-αresponsive metabolite significantly ele...Itaconate,a macrophage-specific anti-inflammatory metabolite,has recently emerged as a critical regulator in rheumatoid arthritis pathogenesis.We found that itaconate is a TNF-αresponsive metabolite significantly elevated in the serum and synovial fluid of rheumatoid arthritis patients and we demonstrated that itaconate is primarily produced by inflammatory macrophages rather than osteoclasts or osteoblasts.In TNF-transgenic and Irg1−/−hybrid mice,a more severe bone destruction phenotype was observed.展开更多
Rheumatoid arthritis(RA)is an autoimmune disease characterized by inflammation and abnormal osteoclast activation,leading to bone destruction.We previously demonstrated that the large extracellular loop(LEL)of Tm4sf19...Rheumatoid arthritis(RA)is an autoimmune disease characterized by inflammation and abnormal osteoclast activation,leading to bone destruction.We previously demonstrated that the large extracellular loop(LEL)of Tm4sf19 is important for its function in osteoclast differentiation,and LEL-Fc,a competitive inhibitor of Tm4sf19,effectively suppresses osteoclast multinucleation and prevent bone loss associated with osteoporosis.This study aimed to investigate the role of Tm4sf19 in RA,an inflammatory and abnormal osteoclast disease,using a mouse model of collagen-induced arthritis(CIA).Tm4sf19 expression was observed in macrophages and osteoclasts within the inflamed synovium,and Tm4sf19 expression was increased together with inflammatory genes in the joint bones of CIA-induced mice compared with the sham control group.Inhibition of Tm4sf19 by LEL-Fc demonstrated both preventive and therapeutic effects in a CIA mouse model,reducing the CIA score,swelling,inflammation,cartilage damage,and bone damage.Knockout of Tm4sf19 gene or inhibition of Tm4sf19 activity by LEL-Fc suppressed LPS/IFN-γ-induced TLR4-mediated inflammatory signaling in macrophages.LEL-Fc disrupted not only the interaction between Tm4sf19 and TLR4/MD2,but also the interaction between TLR4 and MD2.μCT analysis showed that LEL-Fc treatment significantly reduced joint bone destruction and bone loss caused by hyperactivated osteoclasts in CIA mice.Taken together,these findings suggest that LELFc may be a potential treatment for RA and RA-induced osteoporosis by simultaneously targeting joint inflammation and bone destruction caused by abnormal osteoclast activation.展开更多
The use of carbon from waste biomass has the potential to eliminate the drawbacks of Li-S batteries and improve their overall performance.Chrome-tanned-leather-shavings(CTLS)are a readily available waste product that ...The use of carbon from waste biomass has the potential to eliminate the drawbacks of Li-S batteries and improve their overall performance.Chrome-tanned-leather-shavings(CTLS)are a readily available waste product that can be transformed into porous carbon.We prepared an ac-tivated carbon by microwave pyrolysis combined with KOH activator using the CTLS as starting materials.The carbon had a specific surface area of 556 m^(2)g^(-1) and a honeycomb-like structure.Two kinds of N-doped activated carbons were then synthesized by thermal decomposition of the activated carbon,either combined with urea,or impregnated with eth-anolamine.Both N-doped activated carbons have an in-creased number of nitrogen and amine surface groups.However,only the urea treatment was effective in improv-ing the initial capacity of the cell(1363 mAh g^(-1)),which is probably linked to the sorption of long-chain polysulfides.This investigation confirms that it is possible to use the thermal de-composition of urea to obtain carbon materials from CTLS for use as the sulfur-host cathode in Li-S batteries and improve their performance.A radial basis function neural network was fitted to provide statistical support for the experimental results,which confirmed the importance of the nitrogen content of the carbons in determining the discharge capacity of the cells.展开更多
In recent years,numer-ous single-atom catalysts(SACs)have been synthesized to activate persulfate(PS)by a non-radical pathway because of its high se-lectivity,and activity for the cata-lyst.Metal-nitrogen-carbon(M-N_(...In recent years,numer-ous single-atom catalysts(SACs)have been synthesized to activate persulfate(PS)by a non-radical pathway because of its high se-lectivity,and activity for the cata-lyst.Metal-nitrogen-carbon(M-N_(x)-C)has been identified as the key active site in SACs.Although methods for preparing SACs have been extensively reported,a systematic summary of the direct construction of M-N_(x)-C,espe-cially unconventional metal-nitrogen-carbon(UM-N_(x)-C,x≠4),on SACs for PS non-radical activation has still not been reported.The role of the M-N_(x)-C active sites on PS non-radical activation is discussed and methods for the formation of M-N_(x)-C and UM-N_(x)-C active sites in SACs and the effect of catalyst carriers such as carbon nitride(g-C_(3)N_(4)),MOFs,COFs,and other car-bon materials are reviewed.Direct and indirect methods,especially for UM-N_(x)-C active site formation,are also elaborated.Factors affecting the formation of a M-N_(x)-C active site on SACs are also discussed.Prospects for the use of M-N_(x)-C active sites for the non-radical activation of PS by SACs to remove organic contaminants from wastewater are evaluated.展开更多
Advanced oxidation processes(AOPs)governed by peroxide activation to produce highly oxidative active species have been extensively explored for environmental remediation.Nevertheless,the low diffusion rates,inadequate...Advanced oxidation processes(AOPs)governed by peroxide activation to produce highly oxidative active species have been extensively explored for environmental remediation.Nevertheless,the low diffusion rates,inadequate interactions of the reactants,and limited active site exposure hinder treatment efficiency.Porous carbocatalysts with high specific surface area,tunable pore size,and programmable active sites demonstrate outstanding performance in activating diverse types of peroxides to generate active species for treatment of aqueous organic pollutants.The pore-rich structures enhance reaction kinetics for peroxide activation by facilitating diffusion of the reactants and their interactions.Additionally,the structural flexibility of porous structures favors the accommodation of highly dispersed metal species and allows for precise tuning of the microenvironment around the active sites,which further enhances the catalytic activity.This review critically summarizes the recent research progress in the applications of engineered porous carbocatalysts for peroxide activation and outlines the prevailing pore construction methods in carbocatalysts.Moreover,engineering strategies to regulate the mass transfer efficiency and fine-tune the microenvironment around the active sites are systematically addressed to enhance their catalytic peroxide activation performances.Challenges and future research opportunities pertaining to the design,optimization,mechanistic investigation,and practical application of porous carbocatalysts in peroxide activation are also proposed.展开更多
Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to ethylene(C_(2)H_(4))represents a promising approach to reducing CO_(2)emissions and producing high-value chemicals.The ethylene productivity is always limited by t...Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to ethylene(C_(2)H_(4))represents a promising approach to reducing CO_(2)emissions and producing high-value chemicals.The ethylene productivity is always limited by the slow reaction kinetics and the high-performance catalysts are significantly desired.Many efforts have been made to develop a catalyst to activate CO_(2)molecules.However,as another reactant,H2O activation does not receive the attention it deserves.In particular,slow H2O dissociation kinetics limit the rate of proton supply,severely impairing the production of C_(2)H_(4).Here,we designed a MgO-modified CuO catalyst(MgO/CuO),which can promote H2O dissociation and enhance CO_(2)adsorption at the same time to realize the efficient ethylene production.The optimal catalyst exhibits a Faraday efficiency for C_(2)H_(4)reached 54.4%at−1.4 V vs.RHE in an H-cell,which is 1.4 times that of pure CuO(37.9%),and it was further enhanced to a 56.7%in a flow cell,with a high current density of up to 535.9 mA cm−2 at−1.0 V vs.RHE.Experimental and theoretical calculations show that MgO/CuO plays a bifunctional role in the CO_(2)RR,which facilitates the adsorption and activation of CO_(2)by CuO and simultaneously accelerates H2O dissociation by MgO doping.The in situ XRD experiments demonstrate that the introduction of MgO protects CuO active phase to avoid overreduction and preserves the active centers for CO_(2)RR.In combination with in situ FTIR and DFT calculations,the protonation process from*CO to*COH and asymmetric C–C coupling step are promoted by the enhanced water activation and proton coupling on MgO/CuO.This work provides new insights into the CO_(2)and H_(2)O coactivation mechanism in CO_(2)RR and a potential universal strategy to design ethylene production electrocatalysts.展开更多
文摘Biomass-derived carbon materials are favored for their abundance and sustainability,and ease of preparation and modification.By surface activation and modification they can have a good electrical conductivity,excellent catalytic activity,a remarkable adsorption capacity,and different interfacial physicochemical functionalities.Surface-modified biochars have found wide applications in energy storage,environmental remediation,and catalysis.However,achieving precise and controllable modification of their active sites remains a challenge.Recent advances and future prospects for controlling their surface morphology,defect engineering,and surface coating strategies,with particular attention to their means of fabrication,are reviewed.
文摘Rationale:This case report describes a couple with recurrent fertilization failure despite undergoing multiple cycles of intracytoplasmic sperm injection(ICSI).The principal clinical concern was suspected oocyte activation deficiency(OAD),in which fertilization is impeded due to the oocyte’s inability to initiate embryogenesis,commonly attributed to inadequate intracellular calcium(Ca^(2+))release following sperm injection.Patient concerns:The couple repeatedly experienced complete or near-complete fertilization failure in previous ICSI cycles,raising suspicion of an underlying oocyte activation defect.Diagnosis:Based on the repeated absence of fertilization post-ICSI and clinical history,a diagnosis of suspected OAD leading to recurrent ICSI fertilization failure was considered.Interventions:Artificial oocyte activation(AOA)using the calcium ionophore A23187 was performed.After ICSI,unfertilized oocytes were exposed to the ionophore to induce Ca^(2+)influx,simulating physiological calcium oscillations essential for oocyte activation.The efficacy of intervention was evaluated through subsequent embryonic development,morphological grading,and chromosomal integrity.Outcomes:Following AOA treatment,successful oocyte activation occurred,resulting in the formation of high-grade embryos with normal developmental progression.Chromosomal analysis revealed no detectable abnormalities,indicating genomic stability.Lessons:Calcium ionophore–mediated AOA may serve as an effective adjunct in cases of recurrent ICSI failure attributed to OAD.This case highlights the importance of individualized therapeutic strategies in assisted reproduction;however,further research is needed to refine protocols,validate broader clinical efficacy,and assess long-term safety,including potential epigenetic risks.
基金financially supported by the National Natural Science Foundation of China(Nos.52533015,52495013,52403211,52573183,52273157,52073279 and 52025035)Jilin Province,China(Nos.20250601009RC and 20230508102RC)Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2022224)。
文摘Given that platinum-based drugs are widely used clinically as chemotherapeutic agents,their severe toxic side effects have attracted significant attention.Consequently,the development of novel nanoprodrugs based on low-toxicity tetravalent platinum(Pt(Ⅳ))com plexes holds substantial research value.Herein,we discovered that coumarin derivatives exhibit inherent antitumor efficacy and significantly enhance superoxide anion radicals(·O_(2)^(-))generation in aqueous solutions under ultrasound(US)irradiation.Given that·O_(2)^(-)is known to mediate the reduction of Pt(Ⅳ)to divalent platinum(Pt(Ⅱ)),we engineered an US-responsive dual-drug nanoprodrug(P-cisPt(Ⅳ)@5-MOP).This nanoprodrug was prepared by covalently conjugating Pt(Ⅳ)and methoxy polyethylene glycol hydroxyl(m PEG-OH)to a poly(_(L)-glutamic acid)(PLG)carrier,followed by encapsulating coumarin derivatives.Under low-intensity US irradiation(1.5 W/cm^(2),1 MHz,10 min),P-cisPt(Ⅳ)@5-MOP achieved a Pt(Ⅳ)reduction rate of 91.4%.Furthermore,upon US exposure,its half-maximal inhibitory concentration(IC_(50))against 4T1 breast cancer cells decreased dramatically from 25.7μmol/L to 0.1μmol/L.Remarkably,this system combined with US therapy yielded a tumor inhibition rate of 90.9%,with 40%of tumor-bea ring mice achieving com plete eradication of tumors,while exhibiting low systemic toxicity.Collectively,this work not only identifies a novel sonosensitizer capable of generating·O_(2)^(-)but also develops a new class of ultrasound-activatable Pt(Ⅳ)nanoprodrug.
文摘Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt oxyhydroxide @covalent organic frameworks(CoOOH@COFs) S-scheme heterojunction was synthesized,which combined the visible-light-driven photocatalysis and peroxymonosulfate(PMS) activation to synergistically generate abundant reactive oxygen species(ROSs) for TCS degradation.The degradation efficiency of TCS reached 100 % within 8 min in the Vis-CoOOH@COFs/PMS system,and the reaction rate constant was 0.456 min^(-1),which was nearly 1.90 and 2.85 times that of single Co OOH and COFs,and2.36 times that under dark condition,respectively.The density functional theory(DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to Co OOH.Both experimental and theoretical analyses indicated that Co OOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation,enhanced interfacial electron transfer,accelerated PMS activation,and generated multiple ROSs.In particular,photogenerated electrons(e^(-))accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle,while the PMS captured the e-,which significantly decreased the charge combination of Co OOH@COFs.Radicals(O_(2)^(·-),^(·)OH,and SO_(4)^(·-)) and non-radicals(such as ^(1)O_(2),h^(+),and e^(-)) were both presented in the Vis-CoOOH@COFs/PMS system,with O_(2)^(-) playing a dominant role in TCS degradation.Furthermore,the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification.Importantly,the environmentally friendly CoOOH@COFs S-scheme heterojunction exhibited excellent stability and reusability.In conclusion,this study innovatively designed an S-scheme heterojunction in the photocatalytic-PMS activation system,providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
基金supported by the National Key R&D Program of China(2021YFB2401800)the support from Beijing Nova Program(20230484241)+2 种基金the support from the China Postdoctoral Science Foundation(2024M754084)the Postdoctoral Fellowship Program of CPSF(GZB20230931)the support from Initial Energy Science&Technology Co.,Ltd(IEST)。
文摘The dissolution of iron from the cathode and electrode/electrolyte interface(EEI)during long cycles significantly accelerates the aging process of LiFePO_(4)(LFP)/graphite batteries;there is a lack of systematic understanding of the spatial distribution of the EEI interface layer and the dissolve of Fe ions,especially in terms of the mechanism of the cathode-electrolyte interphase(CEI),solid electrolyte interphase(SEI),and iron dissolution.In this study,aged cells were subjected to continuous activation with constant current and multi-step segmented indirect activation(IA)and analyzed for capacity fade,impedance growth,and active Li^(+)mass loss at the EEI and nanoscale levels.The interaction between dissolved Fe^(2+)and the EEI in LFP/graphite pouch batteries was proposed and verified.The findings indicate that during IA process,the electric field facilitates the migration of solvated ions toward the electrodes,while simultaneously inhibiting the formation of organic species such as ROCO_(2)Li.The SEI primarily consists of a mixture of organic and inorganic small molecules,forming a continuous and uniform film on the electrode surface.This study demonstrates that IA favors the formation of a uniform EEI and offers constructive insights for advancing accelerated lifetime prediction strategies in lithium-ion batteries.
基金supported by the NIH RF1 grant NS119477 jointly funded by NINDS and NIA(to RM).
文摘Cells of the central nervous system(CNS)are privileged in lying behind the blood-brain barrier(BBB).Unlike blood vessels in other organs,CNS blood vessels are unique in displaying high electrical resistance and low permeability.With this unique structure and function,the BBB prevents potentially harmful blood components such as serum proteins,inflammatory cytokines,and inflammatory leukocytes from entering the hallowed space of the CNS and wreaking havoc.In addition to these“tightness”properties,the BBB has an array of specialized transporters designed to import essential nutrients.
基金Jane and Aatos Erkko FoundationJenny and Antti Wihuri Foundation for funding
文摘The effect of irreversibly adsorbed Bi on commercial Pt/C catalyst toward glucose electro-oxidation re- action （GOR） in different electrolytes （acidic, neutral, alkaline） is studied. Bi is successfully deposited on Pt/C from Bi3＋ containing acidic solution from 0 to 90% coverage degree. The stability of the Bi layer in acid and alkaline corresponded to previous studies and started to dissolve at 0.7 V and 0.8 V versus re- versible hydrogen electrode （RIIE）, respectively. However, in neutral phosphate buffer the layer showed remarkable stability to at least 1.2V versus RHE. Bi modification at low （20%） and high （80%） coverage showed the highest increase in the activity of Pt/C toward GOR by a factor up to 7 due to the increased poisoning resistance of the modified catalyst. The effect of poisoning was especially reduced at high Bi coverage （80%）, which shows that adsorbate blocked by Bi through the third-body effect is effective. Finally, with or without Bi modification GOR on PtIC was most active in alkaline conditions.
基金Project(50473022) supported by the National Natural Science FoundationProjects(05FJ3080, 2006FJ4100) supported by the Science and Technology Program of Hunan Province, China+2 种基金Project(20060400874) supported by the Postdoctoral Foundation of ChinaProject (2007018) supported by the Foundation of State Key Laboratory of Chemo/Biosensing and Chemometrics of ChinaProject(2006) supported by the Postdoctoral Foundation of Hunan University
文摘After being electro-oxidized by cyclic voltammetry(CV) method in 0.5 mol/L H2SO4 solution or in 0.2 mol/L H2O2+0.5 mol/L H2SO4 solution, the Sn/polyaniline (PANI) electrodes were modified with Pt microparticles by pulse galvanostatic method, thus Pt/Sn hydroxide/PANI electrodes were prepared. The electrocatalytic activities of the Pt/Sn/PANI electrode and Pt/Sn hydroxide/PANI electrode for formaldehyde electro-oxidation were investigated by CV method. The effects of deposition charges (Qdep) of PANI, Sn and Pt, scan rate and formaldehyde concentration on the electrocatalytic activity of Pt/Sn hydroxide/PANI electrode were also studied. The results show that the electrocatalytic activities of the Pt/Sn hydroxide/PANI electrodes are much higher than those of the Pt/Sn/PANI electrode.
基金National Key Research and Development Program of China(2023YFB3810200 to J.L.)National Natural Science Foundation of China(92168204,82225030 to J.L.)Fundamental Research Funds for the Central Universities(22120210586 to J.L.)。
文摘Reproductive hormones associated with the hypothalamic-pituitary-gonadal(HPG)axis are closely linked to bone homeostasis.In this study,we demonstrate that Gonadotropin inhibitory hormone(GnIH,one of the key reproductive hormones upstream of the HPG axis)plays an indispensable role in regulating bone homeostasis and maintaining bone mass.We find that deficiency of GnIH or its receptor Gpr147 leads to a significant reduction in bone mineral density(BMD)in mice primarily by enhancement of osteoclast activation in vivo and in vitro.Mechanistically,GnIH/Gpr147 inhibits osteoclastogenesis by the PI3K/AKT,MAPK,NF-κB and Nfatc1 signaling pathways.Furthermore,GnIH treatment was able to alleviate bone loss in aging,ovariectomy(OVX)or LPS-induced mice.Moreover,the therapy using green light promotes the release of GnIH and rescues OVX-induced bone loss.In humans,serum GnIH increases and bone resorption markers decrease after green light exposure.Therefore,our study elucidates that GnIH plays an important role in maintaining bone homeostasis via modulating osteoclast differentiation and demonstrates the potential of GnIH therapy or green light therapy in preventing osteoporosis.
基金supported by the National Natural Science Foundation of China(No.51602209)the Provincial Nature Science Foundation of Sichuan(No.2016GZ0423,2017CC0017,2018FZ0105)the Fundamental Research Funds supported by Ministry of Education of the People’s Republic of China(No.YJ201746,2018SCUH0025)
文摘To obtain the electrocatalyst with an improved electrocatalytic performance towards formic acid electrooxidation(FAEO), a simple impregnation method is used to prepare Pt3Ni nanoparticles loaded on carbon black, assisted with electrochemically dealloying process. The X-ray powder diffraction(XRD) results as well as transmission electron microscopy(TEM) analysis of as-synthesized electrocatalyst demonstrates that the reduction temperature has a great influence on the FAEO activity of the dealloyed Pt3Ni nanoparticles. X-ray photoelectron spectroscopy(XPS) analyses confirm the variation in the electronic structure of platinum by incorporation of nickel atoms which reduces chemisorption of toxic carbon monoxide and promotes the dehydrogenation pathway of FAEO. The size of the dealloyed Pt3Ni nanoparticles remains within the range of about 2.7 nm. All electrochemical results illustrate that the performance of the asobtained electrocatalyst towards the FAEO is significantly enhanced. Moreover, the carbon black content,incorporation of Ni atoms, and reduction temperature conditions have been proven to be the key factors for modification of the crystal structure and morphology which leads to enhanced catalytic performance.
文摘Calcineurin(CN)is a calcium-and calmodulindependent serine/threonine that has been studied in many model organisms including yeast,filamentous fungi,plants,and mammals.Its biological functions range from ion homeostasis and virulence in lower eukaryotes to T-cell activation in humans by human nuclear factors of activated T-cells.CN is a heterodimeric protein consisting of a catalytic subunit,calcineurin A(Cna1p),which contains an active site with a dinuclear metal center,and a regulatory Ca^(2+) binding subunit called calcineurin B(Cnb1p)required to activate Cna1p.The calcineurin B subunit has been highly conserved through evolution:For example,the mammalian calcineurin B shows 54%identity with calcineurin B from Saccharomyces cerevisiae.
基金supported by the Inner Mongolia Natural Science Foundation(2021MS05064)China Northern Rare Earth Group High-Tech Co.,Ltd.(Bayan Obo rare earth resources extraction and application research and key technology development,2022151).
文摘The La_(1.7)Pr_(0.3)Mg_(16)Ni hydrogen storage alloy was prepared by medium-frequency induction melting,and then the composite hydrogen storage alloy powder of La_(1.7)Pr_(0.3)Mg_(16)Ni+x wt.%(x=0,2,4,and 6)graphene was prepared by ball milling for 10 h.The effect of the addition of graphene on the activation and hydrogen de/absorption properties of La_(1.7)Pr_(0.3)Mg_(16)Ni alloy was studied.The result demonstrated that these composite alloys were composed of La_(2)Mg_(17),La_(2)Ni_(3),and Mg_(2)Ni phases.After saturated hydrogen absorption,it was composed of LaH_(3),Mg_(2)NiH_(4),and MgH_(2)phases,while during the dehydrogenation process,it was composed of LaH_(3),Mg,and Mg_(2)Ni phases.The addition of graphene can help get a more homogeneous granule after ball milling and accelerate the first activation of dehydrogenation/hydrogen absorption.The hydrogen release activation energy of the alloys first decreases and then increases as the graphene content increases from x=0 wt.%to x=6 wt.%.The minimum activation energy of the composite hydrogen storage alloy is 51.22 kJ mol^(-1) when x=4 wt.%.
基金supported by the National Natural Science Foundation of China(52376103,542B2081).
文摘The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development.This study proposes a technique for synthesizing carbon adsorbents using trace KOH-catalyzed CO_(2) activation.Comprehensive investigations were conducted on three aspects:physicochemical structure evolution of biochar,mechanistic understanding of trace KOH-facilitated CO_(2) activation processes,and application characteristics for CO_(2) adsorption.Results demonstrate that biochar activated by trace KOH(<10%)and CO_(2) achieves comparable specific surface area(1244.09 m^(2)/g)to that obtained with 100%KOH activation(1425.10 m^(2)/g).The pore structure characteristics(specific surface area and pore volume)are governed by CO and CH4 generated through K-salt catalyzed reactions between CO_(2) and biochar.The optimal CO_(2) adsorption capacities of KBC adsorbent reached 4.70 mmol/g(0℃)and 7.25 mmol/g(25℃),representing the maximum values among comparable carbon adsorbents.The 5%KBC-CO_(2) sample exhibited CO_(2) adsorption capacities of 3.19 and 5.01 mmol/g under respective conditions,attaining current average performance levels.Notably,CO_(2)/N_(2) selectivity(85∶15,volume ratio)reached 64.71 at 0.02 bar with robust cycling stability.Molecular dynamics simulations revealed that oxygen-containing functional groups accelerate CO_(2) adsorption kinetics and enhance micropore storage capacity.This technical route offers simplicity,environmental compatibility,and scalability,providing critical references for large-scale preparation of high-quality carbon materials.
基金supported by the National Natural Science Foundation of China(No.51972162)the Fundamental Research Funds for the Central Universities(No.2024300440).
文摘Lowering the synthesis temperature of boron nitride nanotubes(BNNTs)is crucial for their development.The primary reason for adopting a high temperature is to enable the effective activation of highmelting-point solid boron.In this study,we developed a novel approach for efficiently activating boron by introducing alkali metal compounds into the conventional MgO–B system.This approach can be adopted to form various low-melting-point AM–Mg–B–O growth systems.These growth systems have improved catalytic capability and reactivity even under low-temperature conditions,facilitating the synthesis of BNNTs at temperatures as low as 850℃.In addition,molecular dynamics simulations based on density functional theory theoretically demonstrate that the systems maintain a liquid state at low temperatures and interact with N atoms to form BN chains.These findings offer novel insights into the design of boron activation and are expected to facilitate research on the low-temperature synthesis of BNNTs.
基金supported by the National Natural Science Foundation of China(NSFC)(No.82130073,No.82372430,No.31871431,No.31821002,No.32101011,No.22177073)Shanghai Frontiers Science Center of Degeneration and Regeneration in Skeletal System+3 种基金Shanghai Science and Technology Committee(No.23ZR1437600,No.24410710600,No.24141901302)Shenzhen Medical Research Fund(No.B2302005)The Open Project Funding of Shanghai Key Laboratory of Orthopedics(No.KFKT202201)Biomaterials and Regenerative Medicine Institute Cooperative,Research Project,Shanghai Jiao Tong University School of Medicine(No.2022LHA01).
文摘Itaconate,a macrophage-specific anti-inflammatory metabolite,has recently emerged as a critical regulator in rheumatoid arthritis pathogenesis.We found that itaconate is a TNF-αresponsive metabolite significantly elevated in the serum and synovial fluid of rheumatoid arthritis patients and we demonstrated that itaconate is primarily produced by inflammatory macrophages rather than osteoclasts or osteoblasts.In TNF-transgenic and Irg1−/−hybrid mice,a more severe bone destruction phenotype was observed.
基金supported by GILO Foundation.This research is in part supported by Korea Drug Development Fund funded by Ministry of Science and ICT,Ministry of Trade,Industry,and Energy,and Ministry of Health and Welfare(RS-2023-00282595,Republic of Korea).
文摘Rheumatoid arthritis(RA)is an autoimmune disease characterized by inflammation and abnormal osteoclast activation,leading to bone destruction.We previously demonstrated that the large extracellular loop(LEL)of Tm4sf19 is important for its function in osteoclast differentiation,and LEL-Fc,a competitive inhibitor of Tm4sf19,effectively suppresses osteoclast multinucleation and prevent bone loss associated with osteoporosis.This study aimed to investigate the role of Tm4sf19 in RA,an inflammatory and abnormal osteoclast disease,using a mouse model of collagen-induced arthritis(CIA).Tm4sf19 expression was observed in macrophages and osteoclasts within the inflamed synovium,and Tm4sf19 expression was increased together with inflammatory genes in the joint bones of CIA-induced mice compared with the sham control group.Inhibition of Tm4sf19 by LEL-Fc demonstrated both preventive and therapeutic effects in a CIA mouse model,reducing the CIA score,swelling,inflammation,cartilage damage,and bone damage.Knockout of Tm4sf19 gene or inhibition of Tm4sf19 activity by LEL-Fc suppressed LPS/IFN-γ-induced TLR4-mediated inflammatory signaling in macrophages.LEL-Fc disrupted not only the interaction between Tm4sf19 and TLR4/MD2,but also the interaction between TLR4 and MD2.μCT analysis showed that LEL-Fc treatment significantly reduced joint bone destruction and bone loss caused by hyperactivated osteoclasts in CIA mice.Taken together,these findings suggest that LELFc may be a potential treatment for RA and RA-induced osteoporosis by simultaneously targeting joint inflammation and bone destruction caused by abnormal osteoclast activation.
文摘The use of carbon from waste biomass has the potential to eliminate the drawbacks of Li-S batteries and improve their overall performance.Chrome-tanned-leather-shavings(CTLS)are a readily available waste product that can be transformed into porous carbon.We prepared an ac-tivated carbon by microwave pyrolysis combined with KOH activator using the CTLS as starting materials.The carbon had a specific surface area of 556 m^(2)g^(-1) and a honeycomb-like structure.Two kinds of N-doped activated carbons were then synthesized by thermal decomposition of the activated carbon,either combined with urea,or impregnated with eth-anolamine.Both N-doped activated carbons have an in-creased number of nitrogen and amine surface groups.However,only the urea treatment was effective in improv-ing the initial capacity of the cell(1363 mAh g^(-1)),which is probably linked to the sorption of long-chain polysulfides.This investigation confirms that it is possible to use the thermal de-composition of urea to obtain carbon materials from CTLS for use as the sulfur-host cathode in Li-S batteries and improve their performance.A radial basis function neural network was fitted to provide statistical support for the experimental results,which confirmed the importance of the nitrogen content of the carbons in determining the discharge capacity of the cells.
文摘In recent years,numer-ous single-atom catalysts(SACs)have been synthesized to activate persulfate(PS)by a non-radical pathway because of its high se-lectivity,and activity for the cata-lyst.Metal-nitrogen-carbon(M-N_(x)-C)has been identified as the key active site in SACs.Although methods for preparing SACs have been extensively reported,a systematic summary of the direct construction of M-N_(x)-C,espe-cially unconventional metal-nitrogen-carbon(UM-N_(x)-C,x≠4),on SACs for PS non-radical activation has still not been reported.The role of the M-N_(x)-C active sites on PS non-radical activation is discussed and methods for the formation of M-N_(x)-C and UM-N_(x)-C active sites in SACs and the effect of catalyst carriers such as carbon nitride(g-C_(3)N_(4)),MOFs,COFs,and other car-bon materials are reviewed.Direct and indirect methods,especially for UM-N_(x)-C active site formation,are also elaborated.Factors affecting the formation of a M-N_(x)-C active site on SACs are also discussed.Prospects for the use of M-N_(x)-C active sites for the non-radical activation of PS by SACs to remove organic contaminants from wastewater are evaluated.
基金supports from the National Natural Science Foundation of China(Nos.22478426 and 22278436)Young Elite Scientists Sponsorship Program by BAST(No.1101020370359)Science Foundation of China University of Petroleum,Beijing(No.2462021QNXZ009)。
文摘Advanced oxidation processes(AOPs)governed by peroxide activation to produce highly oxidative active species have been extensively explored for environmental remediation.Nevertheless,the low diffusion rates,inadequate interactions of the reactants,and limited active site exposure hinder treatment efficiency.Porous carbocatalysts with high specific surface area,tunable pore size,and programmable active sites demonstrate outstanding performance in activating diverse types of peroxides to generate active species for treatment of aqueous organic pollutants.The pore-rich structures enhance reaction kinetics for peroxide activation by facilitating diffusion of the reactants and their interactions.Additionally,the structural flexibility of porous structures favors the accommodation of highly dispersed metal species and allows for precise tuning of the microenvironment around the active sites,which further enhances the catalytic activity.This review critically summarizes the recent research progress in the applications of engineered porous carbocatalysts for peroxide activation and outlines the prevailing pore construction methods in carbocatalysts.Moreover,engineering strategies to regulate the mass transfer efficiency and fine-tune the microenvironment around the active sites are systematically addressed to enhance their catalytic peroxide activation performances.Challenges and future research opportunities pertaining to the design,optimization,mechanistic investigation,and practical application of porous carbocatalysts in peroxide activation are also proposed.
基金supported by the National Natural Science Foundation of China(Grant No.U21B2099,U22A20425,and 22208377)Natural Science Foundation of Shandong Province(ZR2021QE062)Fundamental Research Funds for the Central Universities,Ocean University of China(grant number 202364004)。
文摘Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to ethylene(C_(2)H_(4))represents a promising approach to reducing CO_(2)emissions and producing high-value chemicals.The ethylene productivity is always limited by the slow reaction kinetics and the high-performance catalysts are significantly desired.Many efforts have been made to develop a catalyst to activate CO_(2)molecules.However,as another reactant,H2O activation does not receive the attention it deserves.In particular,slow H2O dissociation kinetics limit the rate of proton supply,severely impairing the production of C_(2)H_(4).Here,we designed a MgO-modified CuO catalyst(MgO/CuO),which can promote H2O dissociation and enhance CO_(2)adsorption at the same time to realize the efficient ethylene production.The optimal catalyst exhibits a Faraday efficiency for C_(2)H_(4)reached 54.4%at−1.4 V vs.RHE in an H-cell,which is 1.4 times that of pure CuO(37.9%),and it was further enhanced to a 56.7%in a flow cell,with a high current density of up to 535.9 mA cm−2 at−1.0 V vs.RHE.Experimental and theoretical calculations show that MgO/CuO plays a bifunctional role in the CO_(2)RR,which facilitates the adsorption and activation of CO_(2)by CuO and simultaneously accelerates H2O dissociation by MgO doping.The in situ XRD experiments demonstrate that the introduction of MgO protects CuO active phase to avoid overreduction and preserves the active centers for CO_(2)RR.In combination with in situ FTIR and DFT calculations,the protonation process from*CO to*COH and asymmetric C–C coupling step are promoted by the enhanced water activation and proton coupling on MgO/CuO.This work provides new insights into the CO_(2)and H_(2)O coactivation mechanism in CO_(2)RR and a potential universal strategy to design ethylene production electrocatalysts.
