Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.展开更多
Electrosynthesis of hydrogen peroxide through the two-electron oxygen reduction pathway provides a crucial alternative to the energy-intensive anthraquinone process.Nevertheless,the efficicency for hydrogen peroxide g...Electrosynthesis of hydrogen peroxide through the two-electron oxygen reduction pathway provides a crucial alternative to the energy-intensive anthraquinone process.Nevertheless,the efficicency for hydrogen peroxide generation is limited by the competitive four-electron pathway.In this work,we report a noncovalent modulation strategy for the isolated CoN_(4) sites by metal-phthalocyanine molecules confinement,which boosts the two-electron oxygen reduction towards generating hydrogen peroxide.The confined Co-phthalocyanine molecules on CoN_(4) sites through π-π interactions induce the competitive*OOH adsorption between the two Co sites formed nanochannel.This noncovalent modulation contributes to the weakened*OOH binding on CoN_(4) sites and thus suppresses its further dissociation,achieving the maximum selectivity of 95% with high activity for H_(2)O_(2)production.This work shows that tailoring noncovalent interactions beyond the binding sites is a promising approach to modulate the local structure of isolated metal sites and related catalytic performance.展开更多
Oxygen reduction reaction(ORR)is crucial for Znair batteries,while also serves as a core electrochemical process in oxygen depolarized cathodes(ODCs)for chlor-alkali electrolysis.The lack of cost-effective,highly acti...Oxygen reduction reaction(ORR)is crucial for Znair batteries,while also serves as a core electrochemical process in oxygen depolarized cathodes(ODCs)for chlor-alkali electrolysis.The lack of cost-effective,highly active ORR electrocatalysts with superior kinetics hinders progress in this field.Herein,we report the Fe/Ni dual single-atomic sites anchored by commercial carbon black(Fe/Ni-N/CB)using rigid ligand confined and high-temperature shock(HTS)strategy in less than 0.5 s.Theoretical calculation reveals that singleatomic Fe is the real active site.Single-atomic Fe and Ni species in Fe/Ni-N/CB synergistically accelerate the kinetics of ORR by reducing the energy barrier of the rate-determining step.A large half-wave potential(E_(1/2))of 0.907 V is achieved in 0.1 M KOH aqueous solution.The assembled aqueous Zn-air battery(A-ZAB)with Fe/Ni-N/CB cathode presents remarkable charge-discharge cycling stability for over 650 h without voltage gap degradation.The quasi-solid-state Zn-air battery(QSS-ZAB)exhibits excellent reversibility over a 150-h operation at 0.5 mA·cm^(-2) with negligible energy conversion efficiency recession.Impressively,Fe/Ni-N/CB||RuO_(2)chloralkali flow cell exhibits a low cell voltage of 1.60 V at a large current density of 300 mA·cm^(-2) at 80℃,and demonstrates exceptional durability with 7% current density decay over 150 h of continuous operation at 100 mA·cm^(-2).Fe/Ni-N/CB||RuO_(2)achieves near-ideal caustic current efficiency(~97.2%)at the current density of 300 mA·cm^(-2).This work provides a rapid and economical synthesis technique for the synthesis of catalysts at the atomic scale while demonstrating significant potential for application in energy-saving chlor-alkali electrolyzer.展开更多
Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active...Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active sites inside the cavity of macrocyclic arenes to better mimic molecular recognition of bioreceptors and enzymes.The editorial aims to enlighten scientists in this field when they develop novel macrocycles for molecular recognition, supramolecular assembly, and applications.展开更多
Single atom catalysts supported by two-dimensional(2D)materials,including graphene,g-C_(3)N_(4),and graphdiyne,ex-hibit promising electrocatalytic nitrogen reduction reaction(NRR)activity.Nevertheless,sometimes theore...Single atom catalysts supported by two-dimensional(2D)materials,including graphene,g-C_(3)N_(4),and graphdiyne,ex-hibit promising electrocatalytic nitrogen reduction reaction(NRR)activity.Nevertheless,sometimes theoretical works failed to predict the high activity of NRR of single atom cat-alysts,especially for Fe,Co,Mn,Cu,Ru.In this work,based on DFT calculations,it is suggested that dual-atom sites on N doped graphene(M_(2)@N-graphene)rather than single-atom sites are more likely to be the active sites for NRR.Notably,Fe_(2)@N_(3),Co_(2)@N_(2),Mn_(2)@N_(2),Cu_(2)@N_(1),and Ru_(2)@N_(3)endow the best catalytic activity with corresponding limiting potentials of-0.26,-0.18,-0.17,-0.39,and-0.30 V,re-spectively.Furthermore,on g-C_(3)N_(4)and graphdiyne,triple-atom sites(TAS,M_(3))such as Ru_(3)(Co_(3))@g-C_(3)N_(4)and Ru_(3)(Rh_(3))@graphdiyne are expected to exhibit higher stability and NRR catalytic performance than single-atom sites(SAS)and dual-atom sites(DAS),with corresponding limiting potentials of-0.28,-0.48,-0.24,and-0.23 V.The calculated results with the corresponding experimental potentials indicate that the origin of superior NRR ac-tivity observed in experiments may be contributed by M_(2)or M_(3)on 2D materials.This study provides an in-depth investigation into real active NRR sites of metal atoms supported on 2D materials and contributes to the design of effective NRR catalysts.展开更多
Gallium nitride(GaN)single crystal with prominent electron mobility and heat resistance have great potential in the high temperature integrate electric power systems.However,the sluggish charge storage kinetics and in...Gallium nitride(GaN)single crystal with prominent electron mobility and heat resistance have great potential in the high temperature integrate electric power systems.However,the sluggish charge storage kinetics and inadequate energy densities are bottlenecks to its practical application.Herein,the self-supported GaN/Mn_(3)O_(4) integrated electrode is developed for both energy harvesting and storage under the high temperature environment.The experimental and theoretical calculations results reveal that such integrated structures with Mn-N heterointerface bring abundant active sites and reconstruct low-energy barrier channels for efficient charge transferring,reasonably optimizing the ions adsorption ability and strengthening the structural stability.Consequently,the assembled GaN based supercapacitors deliver the power density of 34.0 mW cm^(-2) with capacitance retention of 81.3%after 10000 cycles at 130℃.This work innovatively correlates the centimeter scale GaN single crystal with ideal theoretical capacity Mn_(3)O_(4) and provides an effective avenue for the follow-up energy storage applications of the wide bandgap semiconductor.展开更多
Herein,a new type of two-dimensional(2D)/2D Ti_(3)C_(2)/TiO_(2) heterojunction was developed for efficient photocatalytic nitrogen reduction reaction(NRR),in which TiO_(2) nanosheets(TiO_(2) Ns)were designed as the ma...Herein,a new type of two-dimensional(2D)/2D Ti_(3)C_(2)/TiO_(2) heterojunction was developed for efficient photocatalytic nitrogen reduction reaction(NRR),in which TiO_(2) nanosheets(TiO_(2) Ns)were designed as the main catalyst,while Ti_(3)C_(2) MXene served as the co-catalyst.Experimental and theoretical results revealed that Ti_(3)C_(2) MXene introduced electron-rich unsaturated Ti sites,serving as highly active sites for both the adsorption and activation of N_(2) on the Ti_(3)C_(2)/TiO_(2) heterojunction.Furthermore,the 2D/2D Ti_(3)C_(2)/TiO_(2) heterostructure greatly promoted the directional separation and transfer of charge carriers,facilitated by the internal electric field.This structural feature enabled the spatial separation of the N_(2) reduction and H2 O oxidation half-reactions on the distinct surfaces of Ti_(3)C_(2)(001)and TiO_(2)(001),con-sequently reducing the reaction energy barrier for each respective process.The synergistic effects arising from the interface and surface interactions within the heterojunction conspicuously improved the photo-catalytic NRR activity.As a result,the optimized Ti_(3)C_(2)/TiO_(2) heterojunction exhibited a high NH_(3) produc-tion rate of 24.4μmol g−1 h−1 in the absence of sacrificial agents,representing a remarkable 12.8-fold increase compared to individual TiO_(2) Ns.This work provides new insights into rational design of high-performance heterogeneous photocatalysts and offers a deeper understanding of the mechanism under-lying surface active sites in the photocatalytic NRR process.展开更多
Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active...Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.展开更多
The kidney is essential for maintaining fluid,electrolyte,and metabolite homeostasis,and for regulating blood pressure.The pig serves as a valuable biomedical model for human renal physiology,offering insights across ...The kidney is essential for maintaining fluid,electrolyte,and metabolite homeostasis,and for regulating blood pressure.The pig serves as a valuable biomedical model for human renal physiology,offering insights across different physiological states.In this study,single-cell RNA sequencing was used to profile 138469 cells from 12 pig kidney samples collected during the embryonic(E),fattening(F),and pregnancy(P)periods,identifying 29 cell types.Proximal tubule(PT)cells exhibited elevated expression of metabolism-related transcription factors(TFs),including GPD1,ACAA1,and AGMAT,with validation across multiple individuals,periods,and species.Fluorescence homologous double-labeling of paraffin sections further confirmed the expression of ACAA1 and AGMAT in PT cells.Comparative analysis of pig and human kidneys revealed a high degree of similarity among corresponding cell types.Analysis of cell-type heterogeneity highlighted the diversity of thick ascending limb(TAL)cells,identifying a TAL subpopulation related to immune function.Additionally,the functional heterogeneity of kidney-resident macrophages(KRM)was explored across different anatomical sites.In the renal medulla,KRM were implicated in phagocytosis and leukocyte activation,whereas in the renal pelvis,they functioned as ligands,recruiting neutrophils with bactericidal activity to the renal pelvis to combat urinary tract infections.展开更多
The type and quantity of active sites on a catalyst surface determine catalytic activity.In this study,machine learning was employed to assist in the construction of C=O and pyridine N active sites using sludge waste....The type and quantity of active sites on a catalyst surface determine catalytic activity.In this study,machine learning was employed to assist in the construction of C=O and pyridine N active sites using sludge waste.Reactive descriptors,including C%,N%,O%,Fe%,pyrolysis temperature,heating rate,and pyrolysis time were proposed.Decision tree,extra tree,extreme gradient boosting(XGB),automatic relevance determination,and Bayesian ridge regression models were constructed and optimized.Among these,the XGB model was demonstrated with superior accuracy for prediction of C=O sites on the catalyst surface.Additionally,an ensemble model combining extra trees and XGB was developed to predict pyridine N,with R~2 value as high as 0.80 and minimum root mean square error(RMSE)of 0.1386.The ensemble model demonstrated a 17%improvement in accuracy compared to individual models.The model enables high-throughput screening of construction conditions for C=O and pyridine N.The study found that a pyrolysis temperature above of 500–800℃,a heating rate of 10–20℃/min,and a heating time of 120–200 min favor the generation of C=O active sites.For pyridine N sites,a pyrolysis temperature between 400℃ and 600℃,a heating rate of 5–10℃/min,and a pyrolysis time of around 150 min are optimal.Experimental validation demonstrated that both models exhibit excellent predictive performance,with prediction errors below 10%in all cases.This research provides a method to assist in the construction of C=O and pyridine N active sites,which is beneficial for guiding the design of sludge catalysts.展开更多
Two protected sites located on the outskirts of the Sena Oura National Park (PNSO) in West Mayo-Kebbi cover an area of 1800 m2 is pattern choose in pastoral enclave in both village. This study was undertaken to highli...Two protected sites located on the outskirts of the Sena Oura National Park (PNSO) in West Mayo-Kebbi cover an area of 1800 m2 is pattern choose in pastoral enclave in both village. This study was undertaken to highlight the floristic diversity of the herbaceous and woody vegetation on these sites in the offing to know the ability of charge into UBT that most support the park peripheral. It took place on two experimental sites on a natural course in two villages: Wazetelan and Massang. The approach used for the study was a survey using the systematic sampling method and a 30 m × 30 m plot. The survey consisted in listing all the taxa in a floristically homogeneous plot, each assigned the Braun-Blanquet dominance abundance coefficient. These surveys revealed a floristic richness of 73 species, 58 genera, including 46 herbaceous and 26 woody species. The Shannon result gives H1' = 0.12 bit for herbaceous species and H2' = 0.44 bit for woody species, meaning that the herbaceous and woody populations of all the surveys have a very low species diversity, as H' < 3 according to the Shannon index assessment threshold. Herbaceous species are divided into 13 families and 33 genera. The most represented families are Fabaceae (27.3%) and Poaceae (21.9%). Most of the other families (1.3%) have only one species, if any. Herbaceous species are divided into 33 genera grouped into 13 families. The most represented families are Fabaces (16 species), 34%, and Poaceae (12 species), 26%. The 26 woody species, most of which come from itinerant surveys, are distributed across 24 genera and 12 families, the most important of which is Fabaceae with 09 species (34.6%). This floristic assessment, in terms of quantity and quality, has enabled us to estimate the carrying capacity of the two pastoral enclaves in Dari and Goumadji cantons, and to guide the government’s actions with regard to rangeland management.展开更多
As an important pillar of China's industrialization process,the coal industry has not only made contributions to economic growth,but also left a large number of coal mine sites bearing historical memories.These si...As an important pillar of China's industrialization process,the coal industry has not only made contributions to economic growth,but also left a large number of coal mine sites bearing historical memories.These sites are not only the witness of the industrial civilization,but also the potential resources for urban renewal and industrial transformation.展开更多
Enhancing the catalytic hydrolysis efficiency of microcystins(MCs)at ambient temperature has been a persistent challenge in water treatment.We employed N_(2)/low-temperature plasma technology to modify the surface of ...Enhancing the catalytic hydrolysis efficiency of microcystins(MCs)at ambient temperature has been a persistent challenge in water treatment.We employed N_(2)/low-temperature plasma technology to modify the surface of natural pyrites(NP),and the resulting nitrogenmodified pyrites(NPN)with a nanorod structure and new Fe-Nx sites are more efficient for the hydrolysis of microcystins-LR(MC-LR).Kinetic experiments revealed that NPN exhibited significantly higher hydrolysis activity(k_(obs)=0.1471 h^(-1))than NP(0.0914 h^(-1)).Liquid chromatography-mass spectrometry(LC/MS)for the intermediates produced by hydrolyzing MC-LR,in situ attenuated total reflectance Fourier transform infrared spectroscopy(in situ ATR-FTIR)and X-ray photoelectron spectroscopy(XPS)analysis unfolded that the Fe and N atoms of Fe-Nx sites on the surface act of NPN as Lewis acid and Bronsted basic respectively,selectively breaking amide bond on MC-LR molecule.This study demonstrates the effectiveness of plasma technology in modifying mineral materials to enhance their catalytic activity,providing a new method for eliminating MCs in practical water treatment.展开更多
Disrupting the symmetric electron distribution of porphyrin-like Fe singleatom catalysts has been considered as an effective way to harvest high intrinsic activity.Understanding the catalytic performance governed by g...Disrupting the symmetric electron distribution of porphyrin-like Fe singleatom catalysts has been considered as an effective way to harvest high intrinsic activity.Understanding the catalytic performance governed by geometric microstrains is highly desirable for further optimization of such efficient sites.Here,we decipher the crucial role of local microstrain in boosting intrinsic activity and durability of asymmetric Fe single-atom catalysts(Fe-N_(3)S_(1))by replacing one N atom with S atom.The high-curvature hollow carbon nanosphere substrate introduces 1.3%local compressive strain to Fe-N bonds and 1.5%tensile strain to Fe-S bonds,downshifting the d-band center and accelerating the kinetics of*OH reduction.Consequently,highly curved Fe-N_(3)S_(1)sites anchored on hollow carbon nanosphere(FeNS-HNS-20)exhibit negligible current loss,a high half-wave potential of 0.922 V vs.RHE and turnover frequency of 6.2 e^(−1)s^(−1)site−1,which are 53 mV more positive and 1.7 times that of flat Fe-N-S counterpart,respectively.More importantly,multiple operando spectroscopies monitored the dynamic optimization of strained Fe-N_(3)S_(1)sites into Fe-N_(3)sites,further mitigating the overadsorption of*OH intermediates.This work not only sheds new light on local microstrain-induced catalytic enhancement,but also provides a plausible direction for optimizing efficient asymmetric sites via geometric configurations.展开更多
Ground response analysis and determination of site-specific ground motion parameters are necessary for evaluating seismic loads to enable sustainable design of aboveground and underground structures,particularly in de...Ground response analysis and determination of site-specific ground motion parameters are necessary for evaluating seismic loads to enable sustainable design of aboveground and underground structures,particularly in deep overburden sites.This study investigates the influence of bedrock interface conditions and depth of soil deposits on obtained site-specific ground motion parameters.Employing the one-dimensional seismic response analysis program SOILQUAKE,the ground responses of five representative soil profiles and 1050 case studies are calculated considering three different site models of seismic input interfaces.The analysis employs the actual bedrock interface with a shear wave velocity of 760 m/s as the reference input bedrock interface.The results illustrate that the selection of the bedrock interface condition significantly affects the seismic response on the ground surface of deep overburden sites.Specifically,the ground surface acceleration response spectra at longer periods are notably smaller compared to those at the actual bedrock site.This may present a challenge for designing long-period high-rise buildings situated in deep overburden sites.It is recommended to select a seismic input bedrock interface closely approximating the actual bedrock depth when conducting seismic response analyses for deep overburden sites.展开更多
Atomic hydrogen(H∗)plays a crucial role in electrochemical reduction technology towards various environmental and energy applications,but suffers from low utilization efficiency arisen from the undesirable H-H dimeriz...Atomic hydrogen(H∗)plays a crucial role in electrochemical reduction technology towards various environmental and energy applications,but suffers from low utilization efficiency arisen from the undesirable H-H dimerization and the competitive adsorption between water molecule with reactants on the traditional adjacent catalytic sites.Herein,we anchored Pd single atoms on the naturally formed titanium oxide of titanium foam to construct Pd_(1)-O-Ti dual-site electrocatalyst with spatially isolated water dissociation and H∗utilization site,which synchronously inhibits the H-H dimerization and the competitive adsorption of water molecule and targeted reactants.Experiments and theoretical calculations revealed that the Ti-O sites could synergistically dissociate water to H∗,which overflowed to nearby Pd single-atom sites for designed reduction reactions and utilization benefiting from the hydrogen spillover ability of titanium oxide substrate.These Pd_(1)-O-Ti dual sites delivered almost 100%bromate reduction efficiency with a rate constant of 1.57 h^(-1),far superior to those of Pdn-O-Ti with adjacent Pd sites(0.52 h^(-1)),Pd_(1)-N-C with single sites(0.04 h^(-1))and commercial Pd/C(0.18 h^(-1)),respectively.This study sheds light on the importance of integrating synergistic active sites for complicated electrochemical reactions,and provide new insights in improving H∗ utilization for environmental remediation.展开更多
Photocatalytic CO_(2)reduction reaction(CO_(2)RR)is one of the promising strategies for sustainably producing solar fuels.The precise identification of catalytic sites and the enhancement of photocatalytic CO_(2)conve...Photocatalytic CO_(2)reduction reaction(CO_(2)RR)is one of the promising strategies for sustainably producing solar fuels.The precise identification of catalytic sites and the enhancement of photocatalytic CO_(2)conversion is imperative yet quite challenging.This critical review summarizes recent advances in porous photo-responsive polymers,including covalent organic frameworks(COFs),covalent triazine frameworks(CTFs),and conjugated microporous polymers(CMPs),those can be rationally designed from the molecular level for visible-light-driven photocatalytic CO_(2)reduction.Additionally,special emphasis is placed on how the well-defined active sites on these polymers can influence their properties and photocatalytic performance.The precise regulation and control of microenvironments and electronic properties of metal active centers are crucial for boosting catalytic efficiency and selectivity,as well as for the design of better photocatalysts for CO_(2)reduction.展开更多
The electrochemical nitrate reduction reaction(NO_(3)^(-)RR)represents a promising and environmentally friendly approach for both the removal of nitrate(NO_(3)^(-))pollutants and the production of high-value ammonia(N...The electrochemical nitrate reduction reaction(NO_(3)^(-)RR)represents a promising and environmentally friendly approach for both the removal of nitrate(NO_(3)^(-))pollutants and the production of high-value ammonia(NH_(3)).However,this process faces significant challenges in achieving industrial application due to mismatched reaction kinetics involved in the conversion of NO_(3)^(-)to NO_(2)^(-),the formation of active hydrogen(H^(*))via water dissociation,and the stepwise hydrogenation processes.In this study,we developed a trimetallic CuCoRu catalyst with multiple active sites to enhance the selective NH_(3)synthesis at industrial-scale current density,where Cu primarily catalyzes the reduction of NO_(3)^(-)to NO_(2)^(-),Co facilitates the deep hydrogenation of NO_(2)^(-)to NH_(3),and Ru promotes water dissociation to generate H^(*),effectively bridging the aforementioned processes.The optimized CuCoRu catalyst achieves near-100%NH_(3)Faradaic efficiency with an NH_(3)yield rate of 14.6 mmol h^(-1)cm^(-2)at a current density of 2.5 A cm^(-2).The practical application in simulated wastewater with different NO_(3)^(-)concentrations and in the membrane electrode assembly demonstrates great potential for industrial application.展开更多
Lead(Pb)-zinc(Zn)slags contain large amounts of Pb,causing irreversible damage to the environment.Therefore,developing an effective strategy to extract Pb from Pb-Zn slags and convert them into a renewable high-value ...Lead(Pb)-zinc(Zn)slags contain large amounts of Pb,causing irreversible damage to the environment.Therefore,developing an effective strategy to extract Pb from Pb-Zn slags and convert them into a renewable high-value catalyst not only solves the energy crisis but also reduces environmental pollution.Herein,we present a viable strategy to recycle Pb and iron(Fe)from Pb-Zn slags for the fabrication of efficient methylammonium lead tri-iodide(r-MAPbI_(3))piezocatalysts with single-atom Fe-N_(4) sites.Intriguingly,atomically dispersed Fe sites from Pb-Zn slags,which coordinated with N in the neighboring four CH3NH3 to form the FeN_(4) configuration,were detected in the as-obtained r-MAPbI_(3) by synchrotron X-ray absorption spectroscopy.The introduction of Fe single atoms amplified the polarization of MAPbI_(3) and upshifted the d-band center of MAPbI_(3).This not only enhanced the piezoelectric response of MAPbI_(3) but also promoted the proton transfer during the hydrogen evolution process.Due to the decoration of Fe single atoms,r-MAPbI_(3) showed a pronounced H2 yield of 322.4μmol g^(−1) h^(−1),which was 2.52 times that of MAPbI_(3) synthesized using commercially available reagents.This simple yet robust strategy to manufactureMAPbI_(3) piezocatalysts paves a novel way to the large-scale and value-added consumption of Pb-containing waste residues.展开更多
The quest for sustainable energy solutions has intensified the search for alternative feedstocks that can supplement or replace fossil fuels. Obtaining fuels or chemicals through the conversion of renewable biomass is...The quest for sustainable energy solutions has intensified the search for alternative feedstocks that can supplement or replace fossil fuels. Obtaining fuels or chemicals through the conversion of renewable biomass is a promising candidate [1,2]. Some noblemetal-based (e.g., Pt, Pd and Rh) catalysts exhibit significant catalytic activity to the conversion reaction of these biomass.展开更多
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
基金financially supported by the National Natural Science Foundation of China(No.U21A2077)the Natural Science Foundation of Shandong Province(Nos.ZR2022JQ08 and 2023HWYQ-028)+4 种基金the Taishan Scholar Project Foundation of Shandong Province(Nos.tsqn202211028 and tsqn202306080)the City University of Hong Kong(Nos.9020005,9610663,and 7020103)ITF-RTH-Global STEM Professorship(No.9446008)Hong Kong Branch of National Precious Metals Material Engineering Research Center—ITC FundGeneral Research Fund(No.9043720)from the Research Grants Council of Hong Kong SAR,China.
文摘Electrosynthesis of hydrogen peroxide through the two-electron oxygen reduction pathway provides a crucial alternative to the energy-intensive anthraquinone process.Nevertheless,the efficicency for hydrogen peroxide generation is limited by the competitive four-electron pathway.In this work,we report a noncovalent modulation strategy for the isolated CoN_(4) sites by metal-phthalocyanine molecules confinement,which boosts the two-electron oxygen reduction towards generating hydrogen peroxide.The confined Co-phthalocyanine molecules on CoN_(4) sites through π-π interactions induce the competitive*OOH adsorption between the two Co sites formed nanochannel.This noncovalent modulation contributes to the weakened*OOH binding on CoN_(4) sites and thus suppresses its further dissociation,achieving the maximum selectivity of 95% with high activity for H_(2)O_(2)production.This work shows that tailoring noncovalent interactions beyond the binding sites is a promising approach to modulate the local structure of isolated metal sites and related catalytic performance.
基金supported financially by the National Natural Science Foundation of China(No.52172208)Taishan Scholar Young Talent Program(No.tsqn202306216)Shandong Excellent Young Scientists Fund Program(Overseas,2023HWYQ‑091).
文摘Oxygen reduction reaction(ORR)is crucial for Znair batteries,while also serves as a core electrochemical process in oxygen depolarized cathodes(ODCs)for chlor-alkali electrolysis.The lack of cost-effective,highly active ORR electrocatalysts with superior kinetics hinders progress in this field.Herein,we report the Fe/Ni dual single-atomic sites anchored by commercial carbon black(Fe/Ni-N/CB)using rigid ligand confined and high-temperature shock(HTS)strategy in less than 0.5 s.Theoretical calculation reveals that singleatomic Fe is the real active site.Single-atomic Fe and Ni species in Fe/Ni-N/CB synergistically accelerate the kinetics of ORR by reducing the energy barrier of the rate-determining step.A large half-wave potential(E_(1/2))of 0.907 V is achieved in 0.1 M KOH aqueous solution.The assembled aqueous Zn-air battery(A-ZAB)with Fe/Ni-N/CB cathode presents remarkable charge-discharge cycling stability for over 650 h without voltage gap degradation.The quasi-solid-state Zn-air battery(QSS-ZAB)exhibits excellent reversibility over a 150-h operation at 0.5 mA·cm^(-2) with negligible energy conversion efficiency recession.Impressively,Fe/Ni-N/CB||RuO_(2)chloralkali flow cell exhibits a low cell voltage of 1.60 V at a large current density of 300 mA·cm^(-2) at 80℃,and demonstrates exceptional durability with 7% current density decay over 150 h of continuous operation at 100 mA·cm^(-2).Fe/Ni-N/CB||RuO_(2)achieves near-ideal caustic current efficiency(~97.2%)at the current density of 300 mA·cm^(-2).This work provides a rapid and economical synthesis technique for the synthesis of catalysts at the atomic scale while demonstrating significant potential for application in energy-saving chlor-alkali electrolyzer.
文摘Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active sites inside the cavity of macrocyclic arenes to better mimic molecular recognition of bioreceptors and enzymes.The editorial aims to enlighten scientists in this field when they develop novel macrocycles for molecular recognition, supramolecular assembly, and applications.
基金partially supported by the National Natural Science Foundation of China(Nos.22373092,22288201)CAS Project for Young Scientists in Basic Research(YSBR-051)+1 种基金Innovation Program for Quantum Science and Technology(2021ZD0303306)supported by University of Science and Technology of China Tang Scholarship and State Scholarship Fund(202206345005)。
文摘Single atom catalysts supported by two-dimensional(2D)materials,including graphene,g-C_(3)N_(4),and graphdiyne,ex-hibit promising electrocatalytic nitrogen reduction reaction(NRR)activity.Nevertheless,sometimes theoretical works failed to predict the high activity of NRR of single atom cat-alysts,especially for Fe,Co,Mn,Cu,Ru.In this work,based on DFT calculations,it is suggested that dual-atom sites on N doped graphene(M_(2)@N-graphene)rather than single-atom sites are more likely to be the active sites for NRR.Notably,Fe_(2)@N_(3),Co_(2)@N_(2),Mn_(2)@N_(2),Cu_(2)@N_(1),and Ru_(2)@N_(3)endow the best catalytic activity with corresponding limiting potentials of-0.26,-0.18,-0.17,-0.39,and-0.30 V,re-spectively.Furthermore,on g-C_(3)N_(4)and graphdiyne,triple-atom sites(TAS,M_(3))such as Ru_(3)(Co_(3))@g-C_(3)N_(4)and Ru_(3)(Rh_(3))@graphdiyne are expected to exhibit higher stability and NRR catalytic performance than single-atom sites(SAS)and dual-atom sites(DAS),with corresponding limiting potentials of-0.28,-0.48,-0.24,and-0.23 V.The calculated results with the corresponding experimental potentials indicate that the origin of superior NRR ac-tivity observed in experiments may be contributed by M_(2)or M_(3)on 2D materials.This study provides an in-depth investigation into real active NRR sites of metal atoms supported on 2D materials and contributes to the design of effective NRR catalysts.
基金supported by NSFC(Grant No.52202265,52302004,52472010,62434010)the Taishan Scholars Program of Shandong Province(tsqn202306330)+1 种基金Shenzhen Science and Technology Program(JCYJ20230807094009018)Xiaomi Young Talents Program(2023XM06).
文摘Gallium nitride(GaN)single crystal with prominent electron mobility and heat resistance have great potential in the high temperature integrate electric power systems.However,the sluggish charge storage kinetics and inadequate energy densities are bottlenecks to its practical application.Herein,the self-supported GaN/Mn_(3)O_(4) integrated electrode is developed for both energy harvesting and storage under the high temperature environment.The experimental and theoretical calculations results reveal that such integrated structures with Mn-N heterointerface bring abundant active sites and reconstruct low-energy barrier channels for efficient charge transferring,reasonably optimizing the ions adsorption ability and strengthening the structural stability.Consequently,the assembled GaN based supercapacitors deliver the power density of 34.0 mW cm^(-2) with capacitance retention of 81.3%after 10000 cycles at 130℃.This work innovatively correlates the centimeter scale GaN single crystal with ideal theoretical capacity Mn_(3)O_(4) and provides an effective avenue for the follow-up energy storage applications of the wide bandgap semiconductor.
基金supported by the National Natural Science Foundation of China(No.21773089)the Henan Center for Outstanding Overseas Scientist(No.GZS2024004).
文摘Herein,a new type of two-dimensional(2D)/2D Ti_(3)C_(2)/TiO_(2) heterojunction was developed for efficient photocatalytic nitrogen reduction reaction(NRR),in which TiO_(2) nanosheets(TiO_(2) Ns)were designed as the main catalyst,while Ti_(3)C_(2) MXene served as the co-catalyst.Experimental and theoretical results revealed that Ti_(3)C_(2) MXene introduced electron-rich unsaturated Ti sites,serving as highly active sites for both the adsorption and activation of N_(2) on the Ti_(3)C_(2)/TiO_(2) heterojunction.Furthermore,the 2D/2D Ti_(3)C_(2)/TiO_(2) heterostructure greatly promoted the directional separation and transfer of charge carriers,facilitated by the internal electric field.This structural feature enabled the spatial separation of the N_(2) reduction and H2 O oxidation half-reactions on the distinct surfaces of Ti_(3)C_(2)(001)and TiO_(2)(001),con-sequently reducing the reaction energy barrier for each respective process.The synergistic effects arising from the interface and surface interactions within the heterojunction conspicuously improved the photo-catalytic NRR activity.As a result,the optimized Ti_(3)C_(2)/TiO_(2) heterojunction exhibited a high NH_(3) produc-tion rate of 24.4μmol g−1 h−1 in the absence of sacrificial agents,representing a remarkable 12.8-fold increase compared to individual TiO_(2) Ns.This work provides new insights into rational design of high-performance heterogeneous photocatalysts and offers a deeper understanding of the mechanism under-lying surface active sites in the photocatalytic NRR process.
基金supported by Research Grant from China Petroleum and Chemical Corp。
文摘Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.
基金supported by the International Cooperation and Exchange Program of the National Natural Science Foundation of China(32261133531)。
文摘The kidney is essential for maintaining fluid,electrolyte,and metabolite homeostasis,and for regulating blood pressure.The pig serves as a valuable biomedical model for human renal physiology,offering insights across different physiological states.In this study,single-cell RNA sequencing was used to profile 138469 cells from 12 pig kidney samples collected during the embryonic(E),fattening(F),and pregnancy(P)periods,identifying 29 cell types.Proximal tubule(PT)cells exhibited elevated expression of metabolism-related transcription factors(TFs),including GPD1,ACAA1,and AGMAT,with validation across multiple individuals,periods,and species.Fluorescence homologous double-labeling of paraffin sections further confirmed the expression of ACAA1 and AGMAT in PT cells.Comparative analysis of pig and human kidneys revealed a high degree of similarity among corresponding cell types.Analysis of cell-type heterogeneity highlighted the diversity of thick ascending limb(TAL)cells,identifying a TAL subpopulation related to immune function.Additionally,the functional heterogeneity of kidney-resident macrophages(KRM)was explored across different anatomical sites.In the renal medulla,KRM were implicated in phagocytosis and leukocyte activation,whereas in the renal pelvis,they functioned as ligands,recruiting neutrophils with bactericidal activity to the renal pelvis to combat urinary tract infections.
基金supported by the Young Scientific and Technological Talents(Level Two)in Tianjin(No.QN20230214)Climbing Program of Tianjin University(No.2023XPD-0006)+1 种基金National Natural Science Foundation of China(No.52100156)National Engineering Research Center for Digital Construction and Evaluation Technology of Urban Rail Transit(No.2023HJ02)for the financial support。
文摘The type and quantity of active sites on a catalyst surface determine catalytic activity.In this study,machine learning was employed to assist in the construction of C=O and pyridine N active sites using sludge waste.Reactive descriptors,including C%,N%,O%,Fe%,pyrolysis temperature,heating rate,and pyrolysis time were proposed.Decision tree,extra tree,extreme gradient boosting(XGB),automatic relevance determination,and Bayesian ridge regression models were constructed and optimized.Among these,the XGB model was demonstrated with superior accuracy for prediction of C=O sites on the catalyst surface.Additionally,an ensemble model combining extra trees and XGB was developed to predict pyridine N,with R~2 value as high as 0.80 and minimum root mean square error(RMSE)of 0.1386.The ensemble model demonstrated a 17%improvement in accuracy compared to individual models.The model enables high-throughput screening of construction conditions for C=O and pyridine N.The study found that a pyrolysis temperature above of 500–800℃,a heating rate of 10–20℃/min,and a heating time of 120–200 min favor the generation of C=O active sites.For pyridine N sites,a pyrolysis temperature between 400℃ and 600℃,a heating rate of 5–10℃/min,and a pyrolysis time of around 150 min are optimal.Experimental validation demonstrated that both models exhibit excellent predictive performance,with prediction errors below 10%in all cases.This research provides a method to assist in the construction of C=O and pyridine N active sites,which is beneficial for guiding the design of sludge catalysts.
文摘Two protected sites located on the outskirts of the Sena Oura National Park (PNSO) in West Mayo-Kebbi cover an area of 1800 m2 is pattern choose in pastoral enclave in both village. This study was undertaken to highlight the floristic diversity of the herbaceous and woody vegetation on these sites in the offing to know the ability of charge into UBT that most support the park peripheral. It took place on two experimental sites on a natural course in two villages: Wazetelan and Massang. The approach used for the study was a survey using the systematic sampling method and a 30 m × 30 m plot. The survey consisted in listing all the taxa in a floristically homogeneous plot, each assigned the Braun-Blanquet dominance abundance coefficient. These surveys revealed a floristic richness of 73 species, 58 genera, including 46 herbaceous and 26 woody species. The Shannon result gives H1' = 0.12 bit for herbaceous species and H2' = 0.44 bit for woody species, meaning that the herbaceous and woody populations of all the surveys have a very low species diversity, as H' < 3 according to the Shannon index assessment threshold. Herbaceous species are divided into 13 families and 33 genera. The most represented families are Fabaceae (27.3%) and Poaceae (21.9%). Most of the other families (1.3%) have only one species, if any. Herbaceous species are divided into 33 genera grouped into 13 families. The most represented families are Fabaces (16 species), 34%, and Poaceae (12 species), 26%. The 26 woody species, most of which come from itinerant surveys, are distributed across 24 genera and 12 families, the most important of which is Fabaceae with 09 species (34.6%). This floristic assessment, in terms of quantity and quality, has enabled us to estimate the carrying capacity of the two pastoral enclaves in Dari and Goumadji cantons, and to guide the government’s actions with regard to rangeland management.
文摘As an important pillar of China's industrialization process,the coal industry has not only made contributions to economic growth,but also left a large number of coal mine sites bearing historical memories.These sites are not only the witness of the industrial civilization,but also the potential resources for urban renewal and industrial transformation.
基金supported by the National Natural Science Foundation of China(Nos.22076098,22376118 and 21577078)the Outstanding Youth Project of the Natural Science Foundation of Hubei Province(2023AFA054)the 111 Project of China(No.D20015).
文摘Enhancing the catalytic hydrolysis efficiency of microcystins(MCs)at ambient temperature has been a persistent challenge in water treatment.We employed N_(2)/low-temperature plasma technology to modify the surface of natural pyrites(NP),and the resulting nitrogenmodified pyrites(NPN)with a nanorod structure and new Fe-Nx sites are more efficient for the hydrolysis of microcystins-LR(MC-LR).Kinetic experiments revealed that NPN exhibited significantly higher hydrolysis activity(k_(obs)=0.1471 h^(-1))than NP(0.0914 h^(-1)).Liquid chromatography-mass spectrometry(LC/MS)for the intermediates produced by hydrolyzing MC-LR,in situ attenuated total reflectance Fourier transform infrared spectroscopy(in situ ATR-FTIR)and X-ray photoelectron spectroscopy(XPS)analysis unfolded that the Fe and N atoms of Fe-Nx sites on the surface act of NPN as Lewis acid and Bronsted basic respectively,selectively breaking amide bond on MC-LR molecule.This study demonstrates the effectiveness of plasma technology in modifying mineral materials to enhance their catalytic activity,providing a new method for eliminating MCs in practical water treatment.
基金supported by the Natural Science Foundation of Shandong Province (ZR2024JQ004)the National Natural Science Foundation of China (22108306, 22478432)Taishan Scholars Program of Shandong Province
文摘Disrupting the symmetric electron distribution of porphyrin-like Fe singleatom catalysts has been considered as an effective way to harvest high intrinsic activity.Understanding the catalytic performance governed by geometric microstrains is highly desirable for further optimization of such efficient sites.Here,we decipher the crucial role of local microstrain in boosting intrinsic activity and durability of asymmetric Fe single-atom catalysts(Fe-N_(3)S_(1))by replacing one N atom with S atom.The high-curvature hollow carbon nanosphere substrate introduces 1.3%local compressive strain to Fe-N bonds and 1.5%tensile strain to Fe-S bonds,downshifting the d-band center and accelerating the kinetics of*OH reduction.Consequently,highly curved Fe-N_(3)S_(1)sites anchored on hollow carbon nanosphere(FeNS-HNS-20)exhibit negligible current loss,a high half-wave potential of 0.922 V vs.RHE and turnover frequency of 6.2 e^(−1)s^(−1)site−1,which are 53 mV more positive and 1.7 times that of flat Fe-N-S counterpart,respectively.More importantly,multiple operando spectroscopies monitored the dynamic optimization of strained Fe-N_(3)S_(1)sites into Fe-N_(3)sites,further mitigating the overadsorption of*OH intermediates.This work not only sheds new light on local microstrain-induced catalytic enhancement,but also provides a plausible direction for optimizing efficient asymmetric sites via geometric configurations.
基金supported by the National Natural Science Foundation of China(Nos.52408435,52278384)。
文摘Ground response analysis and determination of site-specific ground motion parameters are necessary for evaluating seismic loads to enable sustainable design of aboveground and underground structures,particularly in deep overburden sites.This study investigates the influence of bedrock interface conditions and depth of soil deposits on obtained site-specific ground motion parameters.Employing the one-dimensional seismic response analysis program SOILQUAKE,the ground responses of five representative soil profiles and 1050 case studies are calculated considering three different site models of seismic input interfaces.The analysis employs the actual bedrock interface with a shear wave velocity of 760 m/s as the reference input bedrock interface.The results illustrate that the selection of the bedrock interface condition significantly affects the seismic response on the ground surface of deep overburden sites.Specifically,the ground surface acceleration response spectra at longer periods are notably smaller compared to those at the actual bedrock site.This may present a challenge for designing long-period high-rise buildings situated in deep overburden sites.It is recommended to select a seismic input bedrock interface closely approximating the actual bedrock depth when conducting seismic response analyses for deep overburden sites.
基金supported by the National Natural Science Foundation of China(Nos.U22A20402,U21A20286,and 22102100)the Key Program of Shenzhen Science and Technology Commission(No.JCYJ20220818095601002)the Natural Science Foundation of Shanghai(No.22ZR1431700).
文摘Atomic hydrogen(H∗)plays a crucial role in electrochemical reduction technology towards various environmental and energy applications,but suffers from low utilization efficiency arisen from the undesirable H-H dimerization and the competitive adsorption between water molecule with reactants on the traditional adjacent catalytic sites.Herein,we anchored Pd single atoms on the naturally formed titanium oxide of titanium foam to construct Pd_(1)-O-Ti dual-site electrocatalyst with spatially isolated water dissociation and H∗utilization site,which synchronously inhibits the H-H dimerization and the competitive adsorption of water molecule and targeted reactants.Experiments and theoretical calculations revealed that the Ti-O sites could synergistically dissociate water to H∗,which overflowed to nearby Pd single-atom sites for designed reduction reactions and utilization benefiting from the hydrogen spillover ability of titanium oxide substrate.These Pd_(1)-O-Ti dual sites delivered almost 100%bromate reduction efficiency with a rate constant of 1.57 h^(-1),far superior to those of Pdn-O-Ti with adjacent Pd sites(0.52 h^(-1)),Pd_(1)-N-C with single sites(0.04 h^(-1))and commercial Pd/C(0.18 h^(-1)),respectively.This study sheds light on the importance of integrating synergistic active sites for complicated electrochemical reactions,and provide new insights in improving H∗ utilization for environmental remediation.
基金National Natural Science Foundation of China(No.22005154)for financial support。
文摘Photocatalytic CO_(2)reduction reaction(CO_(2)RR)is one of the promising strategies for sustainably producing solar fuels.The precise identification of catalytic sites and the enhancement of photocatalytic CO_(2)conversion is imperative yet quite challenging.This critical review summarizes recent advances in porous photo-responsive polymers,including covalent organic frameworks(COFs),covalent triazine frameworks(CTFs),and conjugated microporous polymers(CMPs),those can be rationally designed from the molecular level for visible-light-driven photocatalytic CO_(2)reduction.Additionally,special emphasis is placed on how the well-defined active sites on these polymers can influence their properties and photocatalytic performance.The precise regulation and control of microenvironments and electronic properties of metal active centers are crucial for boosting catalytic efficiency and selectivity,as well as for the design of better photocatalysts for CO_(2)reduction.
基金support from the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(22278307,22008170,22222808,21978200)the Haihe Laboratory of Sustainable Chemical Transformations。
文摘The electrochemical nitrate reduction reaction(NO_(3)^(-)RR)represents a promising and environmentally friendly approach for both the removal of nitrate(NO_(3)^(-))pollutants and the production of high-value ammonia(NH_(3)).However,this process faces significant challenges in achieving industrial application due to mismatched reaction kinetics involved in the conversion of NO_(3)^(-)to NO_(2)^(-),the formation of active hydrogen(H^(*))via water dissociation,and the stepwise hydrogenation processes.In this study,we developed a trimetallic CuCoRu catalyst with multiple active sites to enhance the selective NH_(3)synthesis at industrial-scale current density,where Cu primarily catalyzes the reduction of NO_(3)^(-)to NO_(2)^(-),Co facilitates the deep hydrogenation of NO_(2)^(-)to NH_(3),and Ru promotes water dissociation to generate H^(*),effectively bridging the aforementioned processes.The optimized CuCoRu catalyst achieves near-100%NH_(3)Faradaic efficiency with an NH_(3)yield rate of 14.6 mmol h^(-1)cm^(-2)at a current density of 2.5 A cm^(-2).The practical application in simulated wastewater with different NO_(3)^(-)concentrations and in the membrane electrode assembly demonstrates great potential for industrial application.
基金supported by the Foundation for Innovative Research Groups of the National Natural Science Foundation of China(No.52121004,U23B20166)Guangdong Basic and Applied Basic Research Foundation(2024A1515030039,2025A1515010312).
文摘Lead(Pb)-zinc(Zn)slags contain large amounts of Pb,causing irreversible damage to the environment.Therefore,developing an effective strategy to extract Pb from Pb-Zn slags and convert them into a renewable high-value catalyst not only solves the energy crisis but also reduces environmental pollution.Herein,we present a viable strategy to recycle Pb and iron(Fe)from Pb-Zn slags for the fabrication of efficient methylammonium lead tri-iodide(r-MAPbI_(3))piezocatalysts with single-atom Fe-N_(4) sites.Intriguingly,atomically dispersed Fe sites from Pb-Zn slags,which coordinated with N in the neighboring four CH3NH3 to form the FeN_(4) configuration,were detected in the as-obtained r-MAPbI_(3) by synchrotron X-ray absorption spectroscopy.The introduction of Fe single atoms amplified the polarization of MAPbI_(3) and upshifted the d-band center of MAPbI_(3).This not only enhanced the piezoelectric response of MAPbI_(3) but also promoted the proton transfer during the hydrogen evolution process.Due to the decoration of Fe single atoms,r-MAPbI_(3) showed a pronounced H2 yield of 322.4μmol g^(−1) h^(−1),which was 2.52 times that of MAPbI_(3) synthesized using commercially available reagents.This simple yet robust strategy to manufactureMAPbI_(3) piezocatalysts paves a novel way to the large-scale and value-added consumption of Pb-containing waste residues.
文摘The quest for sustainable energy solutions has intensified the search for alternative feedstocks that can supplement or replace fossil fuels. Obtaining fuels or chemicals through the conversion of renewable biomass is a promising candidate [1,2]. Some noblemetal-based (e.g., Pt, Pd and Rh) catalysts exhibit significant catalytic activity to the conversion reaction of these biomass.
