Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidat...Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidative coupling of methane （OCM） to higher hydrocarbons at different reaction conditions （viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1） have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties （viz. surface area, basicity/base strength distribution） and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity （strong basic sites） and the C2＋ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO （Na/Ca = 0.1, before calcination） catalyst （calcined at 750 ℃）, showed best performance （C2＋ selectivity of 68.8% with 24.7% methane conversion）, whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.展开更多
The methane selective oxidation was a"holy grail"reaction.However,peroxidation and low selectivity limited the application.Herein,we combined three Au contents with TiO_(2)in both encapsulation(xAu@TiO_(2))a...The methane selective oxidation was a"holy grail"reaction.However,peroxidation and low selectivity limited the application.Herein,we combined three Au contents with TiO_(2)in both encapsulation(xAu@TiO_(2))and surface-loaded(xAu/TiO_(2))ways by MOF derivation strategy,reported a catalyst 0.5Au@TiO_(2)exhibited a CH_(3)OH yield of 32.5μmol·g^(-1)·h^(-1)and a CH_(3)OH selectivity of 80.6%under catalytic conditions of only CH_(4),O_(2),and H_(2)O.Mechanically speaking,the catalytic activity was controlled by both electron-hole separation efficiency and core-shell structure.The interfacial contact between Au nanoparticles and TiO_(2)in xAu@TiO_(2)and xAu/TiO_(2)induced the formation of oxygen vacancies,with 0.5 Au content showing the highest oxygen vacancy concentration.At the same Au content,xAu@TiO_(2)generated more oxygen vacancies than xAu/TiO_(2).The oxygen vacancy acted as an effective electron cold trap,which enhanced the photogenerated carrier separation efficiency and thereby improved the catalytic activity.In-situ DRIFTs revealed that the isolated OH(non-hydrogen bond adsorption)were key species for the methane selective oxidation,playing a role in the activation of CH_(4)to^(*)CH_(3).However,an overabundance of isolated OH led to severe overoxidation.Fortunately,the core-shell structure over xAu@TiO_(2)provided a slow-release environment for isolated OH through the intermediate state of^(*)OH(hydrogen bond adsorption)to balance the formation rate and consumption rate of isolated OH,doubling the methanol yield and increasing the>29%selectivity.These results showed a new strategy for the control of the overoxidation rate via a strategy of MOF encapsulation followed by pyrolytic derivation for methane selective oxidation.展开更多
BACKGROUND Postoperative delirium(POD)is a common and serious complication in surgical patients,particularly older adults.Alterations in cholinergic function have been implicated in its pathophysiology.AIM To evaluate...BACKGROUND Postoperative delirium(POD)is a common and serious complication in surgical patients,particularly older adults.Alterations in cholinergic function have been implicated in its pathophysiology.AIM To evaluate the association between preoperative serum cholinesterase(ChE)activity—specifically butyrylcholinesterase(BuChE)and acetylcholinesterase(AChE)—and the risk of POD in adult surgical patients in a meta-analysis.METHODS A systematic search was conducted in PubMed,EMBASE,and Web of Science up to March 28,2025 for studies reporting preoperative serum BuChE or AChE activity in relation to subsequent POD incidence.Standardized mean differences(SMDs)and odds ratios(ORs)with 95%confidence intervals(CIs)were pooled using random-effects models.Subgroup and sensitivity analyses were performed based on follow-up duration and analytic models.RESULTS Thirteen studies(n=2730 patients)were included.Patients who developed POD had significantly lower preoperative BuChE activity than those who did not(SMD=-0.28;95%CI:-0.39 to-0.16;I²=18%).Higher BuChE activity was associated with a reduced risk of POD(OR per 100 unit increment=0.97;95%CI:0.95-0.99;I2=0%).In contrast,pooled AChE activity did not differ significantly between POD and non-POD groups(SMD=-0.25;95%CI:-0.53 to 0.03;P=0.08;I2=80%),and the ORs per 1 unit increment in AChE activity were not statistically significant(OR=0.98;95%CI:0.95-1.01).CONCLUSION Lower preoperative serum BuChE activity is associated with an increased risk of POD in adults undergoing surgery.BuChE activity may serve as a potential preoperative biomarker for POD risk stratification.展开更多
BACKGROUND Major depressive disorder(MDD)and obesity(OB)are bidirectionally comorbid conditions with common neurobiological underpinnings.However,the neurocognitive mechanisms of their comorbidity remain poorly unders...BACKGROUND Major depressive disorder(MDD)and obesity(OB)are bidirectionally comorbid conditions with common neurobiological underpinnings.However,the neurocognitive mechanisms of their comorbidity remain poorly understood.AIM To examine regional abnormalities in spontaneous brain activity among patients with MDD-OB comorbidity.METHODS This study adopted a regional homogeneity(ReHo)analysis of resting-state functional magnetic resonance imaging.The study included 149 hospital patients divided into four groups:Patients experiencing their first episode of drug-naive MDD with OB,patients with MDD without OB,and age-and sex-matched healthy individuals with and without OB.Whole-brain ReHo analysis was conducted using SPM12 software and RESTplus toolkits,with group comparisons via ANOVA and post-hoc tests.Correlations between ReHo values and behavioral measures were examined.RESULTS ANOVA revealed significant whole-brain ReHo differences among the four groups in four key regions:The left middle temporal gyrus(MTG.L),right cuneus,left precuneus,and left thalamus.Post-hoc analyses confirmed pairwise differences between all groups across these regions(P<0.05).OB was associated with ReHo alterations in the MTG.L,right cuneus,and left thalamus,whereas abnormalities in the precuneus suggested synergistic pathological mechanisms between MDD and OB.Statistically significant correlations were found between the drive and fun-seeking dimensions of the behavioral activation system,as well as behavioral inhibition and the corresponding ReHo values.CONCLUSION Our findings provide novel evidence for the neuroadaptive mechanisms underlying the MDD-OB comorbidity.Further validation could lead to personalized interventions targeting MTG.L hyperactivity and targeting healthy food cues.展开更多
BACKGROUND Breast cancer is one of the most prevalent malignancies affecting women worldwide,with approximately 2.3 million new cases diagnosed annually.Breast cancer stem cells(BCSCs)play pivotal roles in tumor initi...BACKGROUND Breast cancer is one of the most prevalent malignancies affecting women worldwide,with approximately 2.3 million new cases diagnosed annually.Breast cancer stem cells(BCSCs)play pivotal roles in tumor initiation,progression,metastasis,therapeutic resistance,and disease recurrence.Cancer stem cells possess selfrenewal capacity,multipotent differentiation potential,and enhanced tumorigenic activity,but their molecular characteristics and regulatory mechanisms require further investigation.AIM To comprehensively characterize the molecular features of BCSCs through multiomics approaches,construct a prognostic prediction model based on stem cellrelated genes,reveal cell-cell communication networks within the tumor microenvironment,and provide theoretical foundation for personalized treatment strategies.METHODS Flow cytometry was employed to detect the expression of BCSC surface markers(CD34,CD45,CD29,CD90,CD105).Transcriptomic analysis was performed to identify differentially expressed genes.Least absolute shrinkage and selection operator regression analysis was utilized to screen key prognostic genes and construct a risk scoring model.Single-cell RNA sequencing and spatial transcriptomics were applied to analyze tumor heterogeneity and spatial gene expression patterns.Cell-cell communication network analysis was conducted to reveal interactions between stem cells and the microenvironment.RESULTS Flow cytometric analysis revealed the highest expression of CD105(96.30%),followed by CD90(68.43%)and CD34(62.64%),while CD29 showed lower expression(7.16%)and CD45 exhibited the lowest expression(1.19%).Transcriptomic analysis identified 3837 significantly differentially expressed genes(1478 upregulated and 2359 downregulated).Least absolute shrinkage and selection operator regression analysis selected 10 key prognostic genes,and the constructed risk scoring model effectively distinguished between high-risk and low-risk patient groups(P<0.001).Single-cell analysis revealed tumor cellular heterogeneity,and spatial transcriptomics demonstrated distinct spatial expression gradients of stem cell-related genes.MED18 gene showed significantly higher expression in malignant tissues(P<0.001)and occupied a central position in cell-cell communication networks,exhibiting significant correlations with tumor cells,macrophages,fibroblasts,and endothelial cells.CONCLUSION This study comprehensively characterized the molecular features of BCSCs through multi-omics approaches,identified reliable surface markers and key regulatory genes,and constructed a prognostic prediction model with clinical application value.展开更多
Bimetallic Fe-Mn nano catalysts supported on carbon nanotubes(CNTs) were prepared using microemulsion technique with water-to-surfactant ratios of 0.4-1.6. The nano catalysts were extensively characterized by differen...Bimetallic Fe-Mn nano catalysts supported on carbon nanotubes(CNTs) were prepared using microemulsion technique with water-to-surfactant ratios of 0.4-1.6. The nano catalysts were extensively characterized by different methods and their activity and selectivity in Fischer-Tropsch synthesis(FTS) have been assessed in a fixed-bed microreactor. The physicochemical properties and performance of the nanocatalysts were compared with the catalyst prepared by impregnation method. Very narrow particle size distribution has been produced by the microemulsion technique at relatively high loading of active metal. TEM images showed that small metal nano particles in the range of 3–7 nm were not only confined inside the CNTs but also located on the outer surface of the CNTs. Using microemulsion technique with water to surfactant ratio of0.4 decreased the average iron particle sizes to 5.1 nm. The reduction percentage and dispersion percentage were almost doubled. Activity and selectivity were found to be dependent on the catalyst preparation method and average iron particle size. CO conversion and FTS rate increased from 49.1% to 71.0% and 0.144 to 0.289 gHC/(gcat h), respectively. While the WGS rate decreased from 0.097 to 0.056 gCO2/(gcat h). C5+liquid hydrocarbons selectivity decreased slightly and olefins selectivity almost doubled.展开更多
MnOx-TiO2, CeO2-MnOx-TiO2 and V2O5-MnOx-TiO2 catalysts for low-temperature NH3-SCR were prepared by sol-gel method. The results showed that both cerium and vanadium prevented the transformation ofanatase TiO2 to the m...MnOx-TiO2, CeO2-MnOx-TiO2 and V2O5-MnOx-TiO2 catalysts for low-temperature NH3-SCR were prepared by sol-gel method. The results showed that both cerium and vanadium prevented the transformation ofanatase TiO2 to the mille phase. The addition of vanadium oxide induced the segregation of crystalline Mn2O3, which contributed little to low-temperature SCR and ammonia oxidation, from the MnOx-TiO2 solid solutions. However, the selectivity of the V-containing catalyst was almost 100% due to the decreased ammonia consumption and enhanced adsorption capacity of ammonia on Bronsted acid sites at relatively high temperatures. The electron-donating effect of cerium reduced the Mn^4＋/Mn^3- ratio to some extent, resulting in a decreased activity for ammonia oxidation. This, in combination with the enhanced ammonia adsorption capacity by Ce^n＋ as additional Lewis acid sites, endowed the Ce-doped catalyst a higher N2 selectivity than MnOx-TiO2 despite the slightly elevated light-offtemperamre for NO conversion.展开更多
Active inflammation in“inactive”progressive multiple sclerosis:Traditionally,the distinction between relapsing-remitting multiple sclerosis and progressive multiple sclerosis(PMS)has been framed as an inflammatory v...Active inflammation in“inactive”progressive multiple sclerosis:Traditionally,the distinction between relapsing-remitting multiple sclerosis and progressive multiple sclerosis(PMS)has been framed as an inflammatory versus degenerative dichotomy.This was based on a broad misconception regarding essentially all neurodegenerative conditions,depicting the degenerative process as passive and immune-independent occurring as a late byproduct of active inflammation in the central nervous system(CNS),which is(solely)systemically driven.展开更多
Zero or negative emissions of carbon dioxide(CO2)is the need of the times,as inexorable rising and alarming levels of CO2 in the atmosphere lead to global warming and severe climate change.The electrochemical CO2 redu...Zero or negative emissions of carbon dioxide(CO2)is the need of the times,as inexorable rising and alarming levels of CO2 in the atmosphere lead to global warming and severe climate change.The electrochemical CO2 reduction(eCO2R)to value‐added fuels and chemicals by using renewable electricity provides a cleaner and more sustainable route with economic benefits,in which the key is to develop clean and economical electrocatalysts.Carbon‐based catalyst materials possess desirable properties such as high offset potential for H2 evolution and chemical stability at the negative applied potential.Although it is still challenging to achieve highly efficient carbon‐based catalysts,considerable efforts have been devoted to overcoming the low selectivity,activity,and stability.Here,we summarize and discuss the recent progress in carbon‐based metal‐free catalysts including carbon nanotubes,carbon nanofibers,carbon nanoribbons,graphene,carbon nitride,and diamonds with an emphasis on their activity,product selectivity,and stability.In addition,the key challenges and future potential approaches for efficient eCO2R to low carbon‐based fuels are highlighted.For a good understanding of the whole history of the development of eCO2R,the CO2 reduction reactions,principles,and techniques including the role of electrolytes,electrochemical cell design and evaluation,product selectivity,and structural composition are also discussed.The metal/metal oxides decorated with carbon‐based electrocatalysts are also summarized.We aim to provide insights for further development of carbon‐based metal‐free electrocatalysts for CO2 reduction from the perspective of both fundamental understanding and technological applications in the future.展开更多
The effects of surface strain and subsurface promoters, which are both important factors in heterogeneous catalysis, on catalytic selectivity and activity of Pd are examined in this study by considering the selective ...The effects of surface strain and subsurface promoters, which are both important factors in heterogeneous catalysis, on catalytic selectivity and activity of Pd are examined in this study by considering the selective hydrogenation of acetylene as an example. Combined density functional theory calculations and microkinetic modeling reveal that the selectivity and activity of the Pd catalyst for acetylene hydrogenation can both be substantially influenced by the effects of Pd lattice strain variation and subsurface carbon species formation on the adsorption properties of the reactants and products. It is found that the adsorption energies of the reactants and products are, in general, linearly scaled with the lattice strain for both pristine and subsurface carbon atom-modified Pd（111） surfaces, except for the adsorption of C_2H_2 over Pd（111）-C. The activity for ethylene formation typically corresponds to the region of strong reactants adsorption in the volcano curve; such an effect of lattice strain and the presence of subsurface promoters can improve the activity of the catalyst through the weakening of the adsorption of reactants. The activity and selectivity for Pd（111）-C are always higher than those for the pristine Pd（111） surfaces with respect to ethylene formation. Based on the results obtained, Pd-based catalysts with shrinking lattice constants are suggested as good candidates for the selective hydrogenation of acetylene. A similar approach can be used to facilitate the future design of novel heterogeneous catalysts.展开更多
To improve the activity of Co/Al_(2)O_(3)catalysts in selective catalytic oxidation of ammonia(NH_(3)-SCO),valence state and size of active centers of Al_(2)O_(3)-supported Co catalysts were adjusted by conducting H_(...To improve the activity of Co/Al_(2)O_(3)catalysts in selective catalytic oxidation of ammonia(NH_(3)-SCO),valence state and size of active centers of Al_(2)O_(3)-supported Co catalysts were adjusted by conducting H_(2)reduction pretreatment.The NH_(3)-SCO activity of the adjusted 2Co/Al_(2)O_(3)catalyst was substantially improved,outperforming other catalysts with higher Co-loading.Fresh Co/Al_(2)O_(3)catalysts exhibited multitemperature reduction processes,enabling the control of the valence state of the Co-active centers by adjusting the reduction temperature.Changes in the state of the Co-active centers also led to differences in redox capacity of the catalysts,resulting in different reaction mechanisms for NH_(3)-SCO.However,in situ diffuse reflectance infrared Fourier transform spectra revealed that an excessive O_(2)activation capacity caused overoxidation of NH_(3)to NO and NO_(2).The NH_(3)-SCO activity of the 2Co/Al_(2)O_(3)catalyst with low redox capacity was successfully increased while controlling and optimizing the N_(2)selectivity by modulating the active centers via H_(2)pretreatment,which is a universalmethod used for enhancing the redox properties of catalysts.Thus,this method has great potential for application in the design of inexpensive and highly active catalysts.展开更多
Silica, alumina, and activated carbon supported iron-cobalt catalysts were prepared by incipient wetness impregnation. These catalysts have been characterized by BET, X-ray diffraction （XRD）, and temperature-program...Silica, alumina, and activated carbon supported iron-cobalt catalysts were prepared by incipient wetness impregnation. These catalysts have been characterized by BET, X-ray diffraction （XRD）, and temperature-programmed reduction （TPR）. Activity and selectivity of iron-cobalt supported on different carriers for CO hydrogenation were studied under the conditions of 1.5 MPa, 493 K, 630 h^-1, and H2/CO ratio of 1.6. The results indicate that the activity, C4 olefin/（C4 olefin＋C4 paraffin） ratio, and C5 olefin/（C5 olefin＋C5 paraffin） decrease in the order of Fe-Co/SiO2, Fe-Co/AC1, Fe-Co/Al2O3 and Fe- Co/AC2. The activity of Fe-Co/SiO2 reached a maximum. The results of TPR show that the Fe-Co/SiO2 catalyst is to some extent different. XRD patterns show that the Fe-Co/SiO2 catalyst differs significantly from the others; it has two diffraction peaks. The active spinel phase is correlated with the supports.展开更多
Although coagulase-negative Staphylococcus(CNS),along with technological activities,plays a key role in fermented sausage flavour and nutrient production,the molecular mechanism of these activities remains elusive.In ...Although coagulase-negative Staphylococcus(CNS),along with technological activities,plays a key role in fermented sausage flavour and nutrient production,the molecular mechanism of these activities remains elusive.In this study,18 CNS strains with high proteolytic activity were isolated from Chinese Dong fermented pork(Nanx Wudl),and their technological and transcriptomic properties were investigated.After biochemical identification and genetic analysis,their technological properties,including nitrate reductase,catalase,antioxidant,and lipolytic activities and their growth under varying temperatures,salt concentrations,and p H levels were evaluated.Their aroma-producing potential was also determined in a model medium resembling fermented sausages.Transcriptomic analysis was performed using the most promising isolates.Biochemical identification and 16S rDNA sequencing revealed that the 18 Staphylococcus strains belonged to Staphylococcus xylosus,Staphylococcus saprophyticus,Staphylococcus carnosus,Staphylococcus sciuri,and Staphylococcus equorum.In terms of technological properties,16 strains showed a nitrate-reducing ability,while 11 strains had a lipolytic activity.All strains exhibited superoxide dismutase(SOD)and catalase activities;four strains displayed an SOD activity of>50%.They also tolerated 10%NaCl and 150 mg/kg of nitrite.They showed significant differences in ketone and acid production.The transcriptomic analysis of S.xylosus strains Sx3 and Sx6,which were selected because of their excellent enzymatic activities and aroma-producing ability,revealed the remarkable effect of genes related to pyruvate catabolism and amino acid metabolism on aroma generation.Therefore,this study provided valuable insights into the metabolic mechanisms underlying the technological properties of CNS and identified promising candidates as starter cultures in fermented sausage manufacturing.展开更多
In contrast to heterogeneous network frameworks(e.g.,covalent organic frameworks and metal‐organic frameworks)and porous organic polymers,porous organic cages(POCs)are soluble molecules in common organic solvents tha...In contrast to heterogeneous network frameworks(e.g.,covalent organic frameworks and metal‐organic frameworks)and porous organic polymers,porous organic cages(POCs)are soluble molecules in common organic solvents that provide significant potential for homogeneous catalysis.Herein,we report a triphenylphosphine‐derived quasi‐porous organic cage(denoted as POC‐DICP)as an efficient organic molecular cage ligand for Rh/PPh_(3) system‐catalyzed homogeneous hydroformylation reactions.POC‐DICP not only displays enhanced hydroformylation selectivity(aldehyde selectivity as high as 97%and a linear‐to‐branch ratio as high as 1.89)but can also be recovered and reused via a simple precipitation method in homogeneous reaction systems.We speculate that the reason for the high activity and good selectivity is the favorable geometry(cone angle=123.88°)and electronic effect(P site is relatively electron‐deficient)of POC‐DICP,which were also demonstrated by density functional theory calculations and X‐ray absorption fine‐structure characterization.展开更多
There is an increasing interest in bismuth carbonate(Bi2O2CO3,BOC)as a semiconductor photocatalyst.However,pure BOC strongly absorbs ultraviolet light,which drives a high recombination rate of charge carriers and ther...There is an increasing interest in bismuth carbonate(Bi2O2CO3,BOC)as a semiconductor photocatalyst.However,pure BOC strongly absorbs ultraviolet light,which drives a high recombination rate of charge carriers and thereby limits the overall photocatalysis efficiency.In this work,artificial oxygen vacancies(OV)were introduced into BOC(OV-BOC)to broaden the optical absorption range,increase the charge separation efficiency,and activate the reactants.The photocatalytic removal ratio of NO was increased significantly from 10.0%for pure BOC to 50.2%for OV-BOC because of the multiple roles played by the oxygen vacancies.These results imply that oxygen vacancies can facilitate the electron exchange between intermediates and the surface oxygen vacancies in OV-BOC,making them more easily destroyed by active radicals.In situ DRIFTS spectra in combination with electron spin resonance spectra and density functional theory calculations enabled unraveling of the conversion pathway for the photocatalytic NO oxidation on OV-BOC.It was found that oxygen vacancies could increase the production of active radicals and promote the transformation of NO into target products instead of toxic byproducts(NO2),thus the selectivity is significantly enhanced.This work provides a new strategy for enhancing photocatalytic activity and selectivity.展开更多
Propane oxidative dehydrogenation(ODH)is an energy-efficient approach to produce propylene.However,ODH suff ers from low propylene selectivity due to a relatively higher activation barrier for propylene formation comp...Propane oxidative dehydrogenation(ODH)is an energy-efficient approach to produce propylene.However,ODH suff ers from low propylene selectivity due to a relatively higher activation barrier for propylene formation compared with that for further oxidation.In this work,calculations based on density functional theory were performed to map out the reaction pathways of propane ODH on the surfaces(001)and(010)of nickel oxide hydroxide(NiOOH).Results show that propane is physisorbed on both surfaces and produces propylene through a two-step radical dehydrogenation process.The relatively low activation barriers of propane dehydrogenation on the NiOOH surfaces make the NiOOH-based catalysts promising for propane ODH.By contrast,the weak interaction between the allylic radical and the surface leads to a high activation barrier for further propylene oxidation.These results suggest that the catalysts based on NiOOH can be active and selective for the ODH of propane toward propylene.展开更多
Selective oxidation of saturated C(sp^(3))-H bonds in hydrocarbon to target chemicals under mild conditions remains a signifi-cant but challenging task because of the chemical inertness and high dissociation energy of...Selective oxidation of saturated C(sp^(3))-H bonds in hydrocarbon to target chemicals under mild conditions remains a signifi-cant but challenging task because of the chemical inertness and high dissociation energy of C(sp^(3))-H bonds.Semiconductor photocatalysis can induce the generation of holes and oxidative radicals,off ering an alternative way toward selective oxidation of hydrocarbons under ambient conditions.Herein,we constructed N-doped TiO_(2) nanotubes(N-TNTs)that exhibited remark-able activity and selectivity for toluene oxidation under visible light,delivering the conversion of toluene and selectivity of benzaldehyde of 32% and>99%,respectively.Further mechanistic studies demonstrated that the incorporation of nitrogen induced the generation of N-doping level above the O 2p valance band,directly contributing to the visible-light response of TiO_(2).Furthermore,hydroxyl radicals generated by photogenerated holes at the orbit of O 2p were found to be unselective for the oxidation of toluene,aff ording both benzaldehyde and benzoic acid.The incorporation of nitrogen was able to inhibit the generation of hydroxyl radicals,terminating the formation of benzoic acid.展开更多
C_(2)H_(2)semi-hydrogenation has been widely applied in industry to eliminate trace C_(2)H_(2)from C_(2)H_(4)feed.C_(2)H_(2)semi-hydrogenation to C_(2)H_(4)on a series of the newly designed catalysts,graphdiyne(GDY)as...C_(2)H_(2)semi-hydrogenation has been widely applied in industry to eliminate trace C_(2)H_(2)from C_(2)H_(4)feed.C_(2)H_(2)semi-hydrogenation to C_(2)H_(4)on a series of the newly designed catalysts,graphdiyne(GDY)as a new carbon allotrope supported different sizes of Pd_(x)M_(y)clusters(Pd_(x)M_(y)/GDY,M=Cu,Ag,Au,Ni;x+y=1-3),were studied using DFT calculations.The results found that C_(2)H_(2)semi-hydrogenation to C_(2)H_(4)on Pd_(x)M_(y)/GDY catalysts exhibits that both the activity and selectivity greatly depend on the composition and size of Pd_(x)M_(y)/GDY catalysts.Surprisingly,our results for the first time discovered the Pd_(1)/GDY catalyst with GDY supported the single atom Pd that presents the best selectivity and activity toward C_(2)H_(4)formation compared to the previously reported catalysts so far in C_(2)H_(2)semi-hydrogenation.This study would provide a theoretical clue for designing and screening out the potential catalysts with GDY supported small sizes of Pd_(x)M_(y)and other metal clusters in C_(2)H_(2)hydrogenation.展开更多
Reliable and selective sensing of dopamine(DA)is essential for early diagnosis of mental diseases.Among the various potential methods,nanozyme-based sensing systems have demonstrated promising sensitivity and reliabil...Reliable and selective sensing of dopamine(DA)is essential for early diagnosis of mental diseases.Among the various potential methods,nanozyme-based sensing systems have demonstrated promising sensitivity and reliability.However,owing to the lack of substrate specificity,it is challenging to selectively detect DA using nanozymes.Herein,based on the reactivity of the DA oxidation intermediates,we report a cascade colorimetric sensing system for the selective detection of DA using only a single nanozyme.It was disclosed that the oxidation product of DA catalyzed by Co-N-doped carbon sheets(Co-N-C,a common oxidase-like nanozyme),dopamine quinone(DAQ),showed significant biocatalytic electron-donating activity in the reduction of O_(2)to generate O_(2)·-.Further using O_(2)·-to oxidize3,3,5,5-tetramethylbenzidine(TMB),a colorimetric sensing platform for DA was constructed with a linear detection range of 50 nmol/L to 50μmol/L and a low limit of detection of 4 nmol/L.Thanks to the reactivity of the oxidation product,without any biometric units(such as nucleic acids,enzymes,and antibodies/antigens),the reaction selectivity of DA against other interferences(e.g.,ascorbic acid,adrenaline,5-hydroxytryptamine,and glutathione)was enhanced up to 71-fold.Beyond complicated cascade systems requiring at least two nanozymes,sophisticated artificial recognition via multiple interactions was simplified by exploiting the oxidative properties of product intermediates;thus,only a single common oxidase-like nanozyme was needed.This work offers a new strategy to enhance the selectivity of nanozymes for bioanalytical applications.展开更多
Electrocatalytic nitrate reduction(NO_(3)^(-)RR)offers a promising technique for the removal and utilization of nitrate in water.However,the performance of current catalysts is still limited mainly due to the unfavora...Electrocatalytic nitrate reduction(NO_(3)^(-)RR)offers a promising technique for the removal and utilization of nitrate in water.However,the performance of current catalysts is still limited mainly due to the unfavorable interface that largely determines the reaction efficiency and selectivity.Here we present an in situ dynamic reconstruction strategy to enhance the NO_(3)^(-)RR by constructing Cu/Ce(OH)_(x)catalyst with abundant interfacial active sites.The Cu/Ce(OH)_(x)catalyst was in situ formed through dynamic reconstruction of Cu_(2)Cl(OH)_(3)/Ce(OH)_(x)heterostructure during electrochemical NO_(3)^(‒)RR process.The catalyst exhibits high performance with NO_(3)^(-)conversion of 100.0%,NH_(3)selectivity of 97.8%,NH_(3)Faradaic efficiency of 99.2%and long stability,which is among the state-of-the-art catalysts in neutral media.Both experimental and theoretical results demonstrate that the Cu and Ce sites at the interface can operate cooperatively to promote the adsorption and activation of NO_(3)^(-),and lower the formation energy of key intermediate*HNO.Meanwhile,the hydrogen evolution reaction is also greatly suppressed due to the high H*binding strength at the interface.The strategy can be extended to other catalytic systems and opens a new avenue for the design of efficient electrocatalysts.展开更多
文摘Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidative coupling of methane （OCM） to higher hydrocarbons at different reaction conditions （viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1） have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties （viz. surface area, basicity/base strength distribution） and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity （strong basic sites） and the C2＋ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO （Na/Ca = 0.1, before calcination） catalyst （calcined at 750 ℃）, showed best performance （C2＋ selectivity of 68.8% with 24.7% methane conversion）, whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.
文摘The methane selective oxidation was a"holy grail"reaction.However,peroxidation and low selectivity limited the application.Herein,we combined three Au contents with TiO_(2)in both encapsulation(xAu@TiO_(2))and surface-loaded(xAu/TiO_(2))ways by MOF derivation strategy,reported a catalyst 0.5Au@TiO_(2)exhibited a CH_(3)OH yield of 32.5μmol·g^(-1)·h^(-1)and a CH_(3)OH selectivity of 80.6%under catalytic conditions of only CH_(4),O_(2),and H_(2)O.Mechanically speaking,the catalytic activity was controlled by both electron-hole separation efficiency and core-shell structure.The interfacial contact between Au nanoparticles and TiO_(2)in xAu@TiO_(2)and xAu/TiO_(2)induced the formation of oxygen vacancies,with 0.5 Au content showing the highest oxygen vacancy concentration.At the same Au content,xAu@TiO_(2)generated more oxygen vacancies than xAu/TiO_(2).The oxygen vacancy acted as an effective electron cold trap,which enhanced the photogenerated carrier separation efficiency and thereby improved the catalytic activity.In-situ DRIFTs revealed that the isolated OH(non-hydrogen bond adsorption)were key species for the methane selective oxidation,playing a role in the activation of CH_(4)to^(*)CH_(3).However,an overabundance of isolated OH led to severe overoxidation.Fortunately,the core-shell structure over xAu@TiO_(2)provided a slow-release environment for isolated OH through the intermediate state of^(*)OH(hydrogen bond adsorption)to balance the formation rate and consumption rate of isolated OH,doubling the methanol yield and increasing the>29%selectivity.These results showed a new strategy for the control of the overoxidation rate via a strategy of MOF encapsulation followed by pyrolytic derivation for methane selective oxidation.
文摘BACKGROUND Postoperative delirium(POD)is a common and serious complication in surgical patients,particularly older adults.Alterations in cholinergic function have been implicated in its pathophysiology.AIM To evaluate the association between preoperative serum cholinesterase(ChE)activity—specifically butyrylcholinesterase(BuChE)and acetylcholinesterase(AChE)—and the risk of POD in adult surgical patients in a meta-analysis.METHODS A systematic search was conducted in PubMed,EMBASE,and Web of Science up to March 28,2025 for studies reporting preoperative serum BuChE or AChE activity in relation to subsequent POD incidence.Standardized mean differences(SMDs)and odds ratios(ORs)with 95%confidence intervals(CIs)were pooled using random-effects models.Subgroup and sensitivity analyses were performed based on follow-up duration and analytic models.RESULTS Thirteen studies(n=2730 patients)were included.Patients who developed POD had significantly lower preoperative BuChE activity than those who did not(SMD=-0.28;95%CI:-0.39 to-0.16;I²=18%).Higher BuChE activity was associated with a reduced risk of POD(OR per 100 unit increment=0.97;95%CI:0.95-0.99;I2=0%).In contrast,pooled AChE activity did not differ significantly between POD and non-POD groups(SMD=-0.25;95%CI:-0.53 to 0.03;P=0.08;I2=80%),and the ORs per 1 unit increment in AChE activity were not statistically significant(OR=0.98;95%CI:0.95-1.01).CONCLUSION Lower preoperative serum BuChE activity is associated with an increased risk of POD in adults undergoing surgery.BuChE activity may serve as a potential preoperative biomarker for POD risk stratification.
基金Supported by Provincial Key Research Project of Henan Province,No.232102310081.
文摘BACKGROUND Major depressive disorder(MDD)and obesity(OB)are bidirectionally comorbid conditions with common neurobiological underpinnings.However,the neurocognitive mechanisms of their comorbidity remain poorly understood.AIM To examine regional abnormalities in spontaneous brain activity among patients with MDD-OB comorbidity.METHODS This study adopted a regional homogeneity(ReHo)analysis of resting-state functional magnetic resonance imaging.The study included 149 hospital patients divided into four groups:Patients experiencing their first episode of drug-naive MDD with OB,patients with MDD without OB,and age-and sex-matched healthy individuals with and without OB.Whole-brain ReHo analysis was conducted using SPM12 software and RESTplus toolkits,with group comparisons via ANOVA and post-hoc tests.Correlations between ReHo values and behavioral measures were examined.RESULTS ANOVA revealed significant whole-brain ReHo differences among the four groups in four key regions:The left middle temporal gyrus(MTG.L),right cuneus,left precuneus,and left thalamus.Post-hoc analyses confirmed pairwise differences between all groups across these regions(P<0.05).OB was associated with ReHo alterations in the MTG.L,right cuneus,and left thalamus,whereas abnormalities in the precuneus suggested synergistic pathological mechanisms between MDD and OB.Statistically significant correlations were found between the drive and fun-seeking dimensions of the behavioral activation system,as well as behavioral inhibition and the corresponding ReHo values.CONCLUSION Our findings provide novel evidence for the neuroadaptive mechanisms underlying the MDD-OB comorbidity.Further validation could lead to personalized interventions targeting MTG.L hyperactivity and targeting healthy food cues.
基金the Natural Science Foundation of Yongchuan District,No.2023yc-jckx20021.
文摘BACKGROUND Breast cancer is one of the most prevalent malignancies affecting women worldwide,with approximately 2.3 million new cases diagnosed annually.Breast cancer stem cells(BCSCs)play pivotal roles in tumor initiation,progression,metastasis,therapeutic resistance,and disease recurrence.Cancer stem cells possess selfrenewal capacity,multipotent differentiation potential,and enhanced tumorigenic activity,but their molecular characteristics and regulatory mechanisms require further investigation.AIM To comprehensively characterize the molecular features of BCSCs through multiomics approaches,construct a prognostic prediction model based on stem cellrelated genes,reveal cell-cell communication networks within the tumor microenvironment,and provide theoretical foundation for personalized treatment strategies.METHODS Flow cytometry was employed to detect the expression of BCSC surface markers(CD34,CD45,CD29,CD90,CD105).Transcriptomic analysis was performed to identify differentially expressed genes.Least absolute shrinkage and selection operator regression analysis was utilized to screen key prognostic genes and construct a risk scoring model.Single-cell RNA sequencing and spatial transcriptomics were applied to analyze tumor heterogeneity and spatial gene expression patterns.Cell-cell communication network analysis was conducted to reveal interactions between stem cells and the microenvironment.RESULTS Flow cytometric analysis revealed the highest expression of CD105(96.30%),followed by CD90(68.43%)and CD34(62.64%),while CD29 showed lower expression(7.16%)and CD45 exhibited the lowest expression(1.19%).Transcriptomic analysis identified 3837 significantly differentially expressed genes(1478 upregulated and 2359 downregulated).Least absolute shrinkage and selection operator regression analysis selected 10 key prognostic genes,and the constructed risk scoring model effectively distinguished between high-risk and low-risk patient groups(P<0.001).Single-cell analysis revealed tumor cellular heterogeneity,and spatial transcriptomics demonstrated distinct spatial expression gradients of stem cell-related genes.MED18 gene showed significantly higher expression in malignant tissues(P<0.001)and occupied a central position in cell-cell communication networks,exhibiting significant correlations with tumor cells,macrophages,fibroblasts,and endothelial cells.CONCLUSION This study comprehensively characterized the molecular features of BCSCs through multi-omics approaches,identified reliable surface markers and key regulatory genes,and constructed a prognostic prediction model with clinical application value.
文摘Bimetallic Fe-Mn nano catalysts supported on carbon nanotubes(CNTs) were prepared using microemulsion technique with water-to-surfactant ratios of 0.4-1.6. The nano catalysts were extensively characterized by different methods and their activity and selectivity in Fischer-Tropsch synthesis(FTS) have been assessed in a fixed-bed microreactor. The physicochemical properties and performance of the nanocatalysts were compared with the catalyst prepared by impregnation method. Very narrow particle size distribution has been produced by the microemulsion technique at relatively high loading of active metal. TEM images showed that small metal nano particles in the range of 3–7 nm were not only confined inside the CNTs but also located on the outer surface of the CNTs. Using microemulsion technique with water to surfactant ratio of0.4 decreased the average iron particle sizes to 5.1 nm. The reduction percentage and dispersion percentage were almost doubled. Activity and selectivity were found to be dependent on the catalyst preparation method and average iron particle size. CO conversion and FTS rate increased from 49.1% to 71.0% and 0.144 to 0.289 gHC/(gcat h), respectively. While the WGS rate decreased from 0.097 to 0.056 gCO2/(gcat h). C5+liquid hydrocarbons selectivity decreased slightly and olefins selectivity almost doubled.
基金Project supported by 863 Project (2009AA06Z313,2010CB732304)
文摘MnOx-TiO2, CeO2-MnOx-TiO2 and V2O5-MnOx-TiO2 catalysts for low-temperature NH3-SCR were prepared by sol-gel method. The results showed that both cerium and vanadium prevented the transformation ofanatase TiO2 to the mille phase. The addition of vanadium oxide induced the segregation of crystalline Mn2O3, which contributed little to low-temperature SCR and ammonia oxidation, from the MnOx-TiO2 solid solutions. However, the selectivity of the V-containing catalyst was almost 100% due to the decreased ammonia consumption and enhanced adsorption capacity of ammonia on Bronsted acid sites at relatively high temperatures. The electron-donating effect of cerium reduced the Mn^4＋/Mn^3- ratio to some extent, resulting in a decreased activity for ammonia oxidation. This, in combination with the enhanced ammonia adsorption capacity by Ce^n＋ as additional Lewis acid sites, endowed the Ce-doped catalyst a higher N2 selectivity than MnOx-TiO2 despite the slightly elevated light-offtemperamre for NO conversion.
文摘Active inflammation in“inactive”progressive multiple sclerosis:Traditionally,the distinction between relapsing-remitting multiple sclerosis and progressive multiple sclerosis(PMS)has been framed as an inflammatory versus degenerative dichotomy.This was based on a broad misconception regarding essentially all neurodegenerative conditions,depicting the degenerative process as passive and immune-independent occurring as a late byproduct of active inflammation in the central nervous system(CNS),which is(solely)systemically driven.
基金The authors thank the financial support from the“Scientific and Technical Innovation Action Plan”Basic Research Field of the Shanghai Science and Technology Committee(19JC1410500)the Fundamental ResearchFunds for the Central Universities(2232018A3‐06)the National Natural Science Foundation of China(91645110).
文摘Zero or negative emissions of carbon dioxide(CO2)is the need of the times,as inexorable rising and alarming levels of CO2 in the atmosphere lead to global warming and severe climate change.The electrochemical CO2 reduction(eCO2R)to value‐added fuels and chemicals by using renewable electricity provides a cleaner and more sustainable route with economic benefits,in which the key is to develop clean and economical electrocatalysts.Carbon‐based catalyst materials possess desirable properties such as high offset potential for H2 evolution and chemical stability at the negative applied potential.Although it is still challenging to achieve highly efficient carbon‐based catalysts,considerable efforts have been devoted to overcoming the low selectivity,activity,and stability.Here,we summarize and discuss the recent progress in carbon‐based metal‐free catalysts including carbon nanotubes,carbon nanofibers,carbon nanoribbons,graphene,carbon nitride,and diamonds with an emphasis on their activity,product selectivity,and stability.In addition,the key challenges and future potential approaches for efficient eCO2R to low carbon‐based fuels are highlighted.For a good understanding of the whole history of the development of eCO2R,the CO2 reduction reactions,principles,and techniques including the role of electrolytes,electrochemical cell design and evaluation,product selectivity,and structural composition are also discussed.The metal/metal oxides decorated with carbon‐based electrocatalysts are also summarized.We aim to provide insights for further development of carbon‐based metal‐free electrocatalysts for CO2 reduction from the perspective of both fundamental understanding and technological applications in the future.
基金supported by the National Natural Science Foundation of China(21603142)the Shanghai Pujiang Program(16PJ1406800)the Shanghai Young Eastern Scholar Program(QD2016049)~~
文摘The effects of surface strain and subsurface promoters, which are both important factors in heterogeneous catalysis, on catalytic selectivity and activity of Pd are examined in this study by considering the selective hydrogenation of acetylene as an example. Combined density functional theory calculations and microkinetic modeling reveal that the selectivity and activity of the Pd catalyst for acetylene hydrogenation can both be substantially influenced by the effects of Pd lattice strain variation and subsurface carbon species formation on the adsorption properties of the reactants and products. It is found that the adsorption energies of the reactants and products are, in general, linearly scaled with the lattice strain for both pristine and subsurface carbon atom-modified Pd（111） surfaces, except for the adsorption of C_2H_2 over Pd（111）-C. The activity for ethylene formation typically corresponds to the region of strong reactants adsorption in the volcano curve; such an effect of lattice strain and the presence of subsurface promoters can improve the activity of the catalyst through the weakening of the adsorption of reactants. The activity and selectivity for Pd（111）-C are always higher than those for the pristine Pd（111） surfaces with respect to ethylene formation. Based on the results obtained, Pd-based catalysts with shrinking lattice constants are suggested as good candidates for the selective hydrogenation of acetylene. A similar approach can be used to facilitate the future design of novel heterogeneous catalysts.
基金supported by the National Natural Science Foundation of China(No.52260013)Yunnan Major Scientific and Technological Projects(No.202202AG050005).
文摘To improve the activity of Co/Al_(2)O_(3)catalysts in selective catalytic oxidation of ammonia(NH_(3)-SCO),valence state and size of active centers of Al_(2)O_(3)-supported Co catalysts were adjusted by conducting H_(2)reduction pretreatment.The NH_(3)-SCO activity of the adjusted 2Co/Al_(2)O_(3)catalyst was substantially improved,outperforming other catalysts with higher Co-loading.Fresh Co/Al_(2)O_(3)catalysts exhibited multitemperature reduction processes,enabling the control of the valence state of the Co-active centers by adjusting the reduction temperature.Changes in the state of the Co-active centers also led to differences in redox capacity of the catalysts,resulting in different reaction mechanisms for NH_(3)-SCO.However,in situ diffuse reflectance infrared Fourier transform spectra revealed that an excessive O_(2)activation capacity caused overoxidation of NH_(3)to NO and NO_(2).The NH_(3)-SCO activity of the 2Co/Al_(2)O_(3)catalyst with low redox capacity was successfully increased while controlling and optimizing the N_(2)selectivity by modulating the active centers via H_(2)pretreatment,which is a universalmethod used for enhancing the redox properties of catalysts.Thus,this method has great potential for application in the design of inexpensive and highly active catalysts.
文摘Silica, alumina, and activated carbon supported iron-cobalt catalysts were prepared by incipient wetness impregnation. These catalysts have been characterized by BET, X-ray diffraction （XRD）, and temperature-programmed reduction （TPR）. Activity and selectivity of iron-cobalt supported on different carriers for CO hydrogenation were studied under the conditions of 1.5 MPa, 493 K, 630 h^-1, and H2/CO ratio of 1.6. The results indicate that the activity, C4 olefin/（C4 olefin＋C4 paraffin） ratio, and C5 olefin/（C5 olefin＋C5 paraffin） decrease in the order of Fe-Co/SiO2, Fe-Co/AC1, Fe-Co/Al2O3 and Fe- Co/AC2. The activity of Fe-Co/SiO2 reached a maximum. The results of TPR show that the Fe-Co/SiO2 catalyst is to some extent different. XRD patterns show that the Fe-Co/SiO2 catalyst differs significantly from the others; it has two diffraction peaks. The active spinel phase is correlated with the supports.
基金the financial support of the National Natural Science Foundation of China(32102016)the Taishan Industrial Experts Program。
文摘Although coagulase-negative Staphylococcus(CNS),along with technological activities,plays a key role in fermented sausage flavour and nutrient production,the molecular mechanism of these activities remains elusive.In this study,18 CNS strains with high proteolytic activity were isolated from Chinese Dong fermented pork(Nanx Wudl),and their technological and transcriptomic properties were investigated.After biochemical identification and genetic analysis,their technological properties,including nitrate reductase,catalase,antioxidant,and lipolytic activities and their growth under varying temperatures,salt concentrations,and p H levels were evaluated.Their aroma-producing potential was also determined in a model medium resembling fermented sausages.Transcriptomic analysis was performed using the most promising isolates.Biochemical identification and 16S rDNA sequencing revealed that the 18 Staphylococcus strains belonged to Staphylococcus xylosus,Staphylococcus saprophyticus,Staphylococcus carnosus,Staphylococcus sciuri,and Staphylococcus equorum.In terms of technological properties,16 strains showed a nitrate-reducing ability,while 11 strains had a lipolytic activity.All strains exhibited superoxide dismutase(SOD)and catalase activities;four strains displayed an SOD activity of>50%.They also tolerated 10%NaCl and 150 mg/kg of nitrite.They showed significant differences in ketone and acid production.The transcriptomic analysis of S.xylosus strains Sx3 and Sx6,which were selected because of their excellent enzymatic activities and aroma-producing ability,revealed the remarkable effect of genes related to pyruvate catabolism and amino acid metabolism on aroma generation.Therefore,this study provided valuable insights into the metabolic mechanisms underlying the technological properties of CNS and identified promising candidates as starter cultures in fermented sausage manufacturing.
文摘In contrast to heterogeneous network frameworks(e.g.,covalent organic frameworks and metal‐organic frameworks)and porous organic polymers,porous organic cages(POCs)are soluble molecules in common organic solvents that provide significant potential for homogeneous catalysis.Herein,we report a triphenylphosphine‐derived quasi‐porous organic cage(denoted as POC‐DICP)as an efficient organic molecular cage ligand for Rh/PPh_(3) system‐catalyzed homogeneous hydroformylation reactions.POC‐DICP not only displays enhanced hydroformylation selectivity(aldehyde selectivity as high as 97%and a linear‐to‐branch ratio as high as 1.89)but can also be recovered and reused via a simple precipitation method in homogeneous reaction systems.We speculate that the reason for the high activity and good selectivity is the favorable geometry(cone angle=123.88°)and electronic effect(P site is relatively electron‐deficient)of POC‐DICP,which were also demonstrated by density functional theory calculations and X‐ray absorption fine‐structure characterization.
基金supported by the National Key R&D Program of China(2016YFC02047)the National Natural Science Foundation of China(21822601,21777011,and 21501016)+3 种基金the Graduate Research and Innovation Foundation of Chongqing(CYS18019)the Innovative Research Team of Chongqing(CXTDG201602014)the Natural Science Foundation of Chongqing(cstc2017jcyjBX0052)the National Special Supporting National Plan for High-Level~~
文摘There is an increasing interest in bismuth carbonate(Bi2O2CO3,BOC)as a semiconductor photocatalyst.However,pure BOC strongly absorbs ultraviolet light,which drives a high recombination rate of charge carriers and thereby limits the overall photocatalysis efficiency.In this work,artificial oxygen vacancies(OV)were introduced into BOC(OV-BOC)to broaden the optical absorption range,increase the charge separation efficiency,and activate the reactants.The photocatalytic removal ratio of NO was increased significantly from 10.0%for pure BOC to 50.2%for OV-BOC because of the multiple roles played by the oxygen vacancies.These results imply that oxygen vacancies can facilitate the electron exchange between intermediates and the surface oxygen vacancies in OV-BOC,making them more easily destroyed by active radicals.In situ DRIFTS spectra in combination with electron spin resonance spectra and density functional theory calculations enabled unraveling of the conversion pathway for the photocatalytic NO oxidation on OV-BOC.It was found that oxygen vacancies could increase the production of active radicals and promote the transformation of NO into target products instead of toxic byproducts(NO2),thus the selectivity is significantly enhanced.This work provides a new strategy for enhancing photocatalytic activity and selectivity.
基金the National Natural Science Foundation of China(Nos.21873067 and 21576204).
文摘Propane oxidative dehydrogenation(ODH)is an energy-efficient approach to produce propylene.However,ODH suff ers from low propylene selectivity due to a relatively higher activation barrier for propylene formation compared with that for further oxidation.In this work,calculations based on density functional theory were performed to map out the reaction pathways of propane ODH on the surfaces(001)and(010)of nickel oxide hydroxide(NiOOH).Results show that propane is physisorbed on both surfaces and produces propylene through a two-step radical dehydrogenation process.The relatively low activation barriers of propane dehydrogenation on the NiOOH surfaces make the NiOOH-based catalysts promising for propane ODH.By contrast,the weak interaction between the allylic radical and the surface leads to a high activation barrier for further propylene oxidation.These results suggest that the catalysts based on NiOOH can be active and selective for the ODH of propane toward propylene.
基金the National Natural Science Foundation of China(Nos.22025206,21991094)supported by the Ministry of ScienceTechnology of the People’s Republic of China(No.2018YFE0118100)+1 种基金the CAS-NSTDA Joint Research Project(No.GJHZ2075)Dalian Science and Technology Innovation Fund(No.2019J11CY009).
文摘Selective oxidation of saturated C(sp^(3))-H bonds in hydrocarbon to target chemicals under mild conditions remains a signifi-cant but challenging task because of the chemical inertness and high dissociation energy of C(sp^(3))-H bonds.Semiconductor photocatalysis can induce the generation of holes and oxidative radicals,off ering an alternative way toward selective oxidation of hydrocarbons under ambient conditions.Herein,we constructed N-doped TiO_(2) nanotubes(N-TNTs)that exhibited remark-able activity and selectivity for toluene oxidation under visible light,delivering the conversion of toluene and selectivity of benzaldehyde of 32% and>99%,respectively.Further mechanistic studies demonstrated that the incorporation of nitrogen induced the generation of N-doping level above the O 2p valance band,directly contributing to the visible-light response of TiO_(2).Furthermore,hydroxyl radicals generated by photogenerated holes at the orbit of O 2p were found to be unselective for the oxidation of toluene,aff ording both benzaldehyde and benzoic acid.The incorporation of nitrogen was able to inhibit the generation of hydroxyl radicals,terminating the formation of benzoic acid.
基金financially supported by the National Natural Science Foundation of China(No.21776193 and 21736007)U.S.NSF-sponsored NCAR-Wyoming Supercomputing Center(NWSC)。
文摘C_(2)H_(2)semi-hydrogenation has been widely applied in industry to eliminate trace C_(2)H_(2)from C_(2)H_(4)feed.C_(2)H_(2)semi-hydrogenation to C_(2)H_(4)on a series of the newly designed catalysts,graphdiyne(GDY)as a new carbon allotrope supported different sizes of Pd_(x)M_(y)clusters(Pd_(x)M_(y)/GDY,M=Cu,Ag,Au,Ni;x+y=1-3),were studied using DFT calculations.The results found that C_(2)H_(2)semi-hydrogenation to C_(2)H_(4)on Pd_(x)M_(y)/GDY catalysts exhibits that both the activity and selectivity greatly depend on the composition and size of Pd_(x)M_(y)/GDY catalysts.Surprisingly,our results for the first time discovered the Pd_(1)/GDY catalyst with GDY supported the single atom Pd that presents the best selectivity and activity toward C_(2)H_(4)formation compared to the previously reported catalysts so far in C_(2)H_(2)semi-hydrogenation.This study would provide a theoretical clue for designing and screening out the potential catalysts with GDY supported small sizes of Pd_(x)M_(y)and other metal clusters in C_(2)H_(2)hydrogenation.
基金supported by the National Natural Science Foundation of China(Nos.22174014 and 22074015)。
文摘Reliable and selective sensing of dopamine(DA)is essential for early diagnosis of mental diseases.Among the various potential methods,nanozyme-based sensing systems have demonstrated promising sensitivity and reliability.However,owing to the lack of substrate specificity,it is challenging to selectively detect DA using nanozymes.Herein,based on the reactivity of the DA oxidation intermediates,we report a cascade colorimetric sensing system for the selective detection of DA using only a single nanozyme.It was disclosed that the oxidation product of DA catalyzed by Co-N-doped carbon sheets(Co-N-C,a common oxidase-like nanozyme),dopamine quinone(DAQ),showed significant biocatalytic electron-donating activity in the reduction of O_(2)to generate O_(2)·-.Further using O_(2)·-to oxidize3,3,5,5-tetramethylbenzidine(TMB),a colorimetric sensing platform for DA was constructed with a linear detection range of 50 nmol/L to 50μmol/L and a low limit of detection of 4 nmol/L.Thanks to the reactivity of the oxidation product,without any biometric units(such as nucleic acids,enzymes,and antibodies/antigens),the reaction selectivity of DA against other interferences(e.g.,ascorbic acid,adrenaline,5-hydroxytryptamine,and glutathione)was enhanced up to 71-fold.Beyond complicated cascade systems requiring at least two nanozymes,sophisticated artificial recognition via multiple interactions was simplified by exploiting the oxidative properties of product intermediates;thus,only a single common oxidase-like nanozyme was needed.This work offers a new strategy to enhance the selectivity of nanozymes for bioanalytical applications.
文摘Electrocatalytic nitrate reduction(NO_(3)^(-)RR)offers a promising technique for the removal and utilization of nitrate in water.However,the performance of current catalysts is still limited mainly due to the unfavorable interface that largely determines the reaction efficiency and selectivity.Here we present an in situ dynamic reconstruction strategy to enhance the NO_(3)^(-)RR by constructing Cu/Ce(OH)_(x)catalyst with abundant interfacial active sites.The Cu/Ce(OH)_(x)catalyst was in situ formed through dynamic reconstruction of Cu_(2)Cl(OH)_(3)/Ce(OH)_(x)heterostructure during electrochemical NO_(3)^(‒)RR process.The catalyst exhibits high performance with NO_(3)^(-)conversion of 100.0%,NH_(3)selectivity of 97.8%,NH_(3)Faradaic efficiency of 99.2%and long stability,which is among the state-of-the-art catalysts in neutral media.Both experimental and theoretical results demonstrate that the Cu and Ce sites at the interface can operate cooperatively to promote the adsorption and activation of NO_(3)^(-),and lower the formation energy of key intermediate*HNO.Meanwhile,the hydrogen evolution reaction is also greatly suppressed due to the high H*binding strength at the interface.The strategy can be extended to other catalytic systems and opens a new avenue for the design of efficient electrocatalysts.
