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
Directional catalytic transformation of volatile organic compounds(VOCs)into value-added chemicals represents a more sustainable strategy than complete mineralization,as it simultaneously mitigates environmental pollu...Directional catalytic transformation of volatile organic compounds(VOCs)into value-added chemicals represents a more sustainable strategy than complete mineralization,as it simultaneously mitigates environmental pollution and reduces carbon emissions.The primary challenge in achieving multifunctional olefin production from alcohol-type VOCs is the lack of mechanistic clarity,which hinders the targeted synthesis of selective catalysts.Herein,we developed W-Ti hybrid metal oxide catalysts(WTiO_(x))with active Ti-O-W interfaces via a one-step hydrothermal synthesis and demonstrated their effectiveness for isopropanol conversion processes.Remarkably,WTiO_(x)-500 achieved 99.8%isopropanol conversion and 99.3% propylene yield at 140℃,significantly outperforming TiO_(2)(98.4% yield at 180℃)and WO_(3)(90.5% yield at 240℃).WTiO_(x)-500 also displayed higher thermal stability,with isopropanol conversion and propylene yield decreasing by 1.0%and 1.6% after 35 h on-stream reaction.Although impurities(e.g.,CO_(2),HCl,SO_(2))caused partial deactivation of WTiO_(x)-500,oxygen treatment regenerated the catalyst.A series of characterization techniques indicated that the controlled calcination temperature promoted the formation of an optimal Ti-O-Winterface in WTiO_(x)-500 through W substitution into the TiO_(2)lattice and WO_(3)-TiO_(2)surface interaction,where W species effectively tuned the electronic structure.This configuration endowed WTiO_(x)-500 with moderate acidity of BrФnsted(-OH)and Lewis(Ti^(4+)/W^(6+))acid sites,which synergistically facilitated charge transfer between isopropanol and catalyst,accelerated C-O bond cleavage during dehydration.This work provides mechanistic insights into isopropanol dehydration and demonstrates a potential approach for VOC valorization.展开更多
Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.展开更多
Peroxymonosulfate(PMS)-based advanced oxidation technology has been proven to be a viable option for the decontamination of organic pollutants from water bodies.Advanced catalyst design is essential to this technology...Peroxymonosulfate(PMS)-based advanced oxidation technology has been proven to be a viable option for the decontamination of organic pollutants from water bodies.Advanced catalyst design is essential to this technology.Herein,a vanadium-doped LaFeO_(3) perovskite(LFO-V)featuring asymmetric Fe-O-V sites was rationally designed.Thanks to orbital electron interaction between Fe and V atoms,the modified electronic structure elevated electron density near the Fermi energy level while reducing the energy barrier toward effective PMS activation.This facilitated concurrent PMS reduction at the Fe sites to generate SO_(4)^(·-)and·OH(57.7%),and PMS oxidation at V sites to produce ^(1)O_(2)(42.3%).The LFO-V/PMS system demonstrated excellent tetracycline(TC)degradation performance with a 2-fold enhancement in rate constant compared to that of pristine LFO.Further,the LFO-V maintained long-term stability,and the toxicity of degradation intermediates was evaluated through microbial metabolomics.This work establishes an effective route to regulate the PMS activation pathways through precise electronic structure modulation,advancing the rational design of advanced Fenton-like catalysts.展开更多
Seawater electrolysis has attracted considerable attention in hydrogen production.However,the chloride ions(Cl^(-))in seawater can corrode metal sites and decrease the lifespans of the oxygen evolution reaction(OER).H...Seawater electrolysis has attracted considerable attention in hydrogen production.However,the chloride ions(Cl^(-))in seawater can corrode metal sites and decrease the lifespans of the oxygen evolution reaction(OER).Herein,we report a reversed-active sites strategy,converting Cl^(-)-affinitive metal sites to Cl^(-)-repellent oxygen sites,for OER in alkaline seawater electrolysis.First,ex/in situ experiments confirm the effectiveness of such a strategy using typical perovskites following the adsorbate evolution mechanism(AEM)or lattice oxygen-mediated mechanism(LOM).Furthermore,the origins of the superior activity and durability of as-prepared La_(0.3)SrCo_(0.5)Fe_(0.5)Ox(La_(0.3))can be ascribed to higher participation of lattice oxygen in OER,rapid bulk oxygen diffusion,and excellent OH-adsorption kinetics.Hence,an alkaline seawater electrolytic cell with La_(0.3)as the anode produces 10 mA cm^(-2)at just 1.57 V and maintains near-constant activity over 150 hours.This work introduces novel concepts for the production of superactive and steady electrocatalysts for the electrolysis of seawater.展开更多
Large-scale CO_(2)emissions have exacerbated the greenhouse effect,reinforcing the critical need for efficient CO_(2)mitigation methods.Plasma-catalytic technology enables CO_(2)conversion under mild conditions,especi...Large-scale CO_(2)emissions have exacerbated the greenhouse effect,reinforcing the critical need for efficient CO_(2)mitigation methods.Plasma-catalytic technology enables CO_(2)conversion under mild conditions,especially for CO_(2)methanation(the Sabatier reaction),which has attracted significant attention due to its economic benefits and the potential for safe energy transportation via existing natural gas pipelines.The development of high-performance CO_(2)methanation catalysts remains an ongoing and long-term objective,and there is a lack of adequate in-situ characterization techniques to investigate the mechanisms.This study focuses on the Ni/La_(2)O_(3)(LN)catalyst and introduces two CO_(2)activation strategies through F and Na modifications:the Ni-Ov-Ni site activation with electron transfer from Ni0 under low-power conditions and basic site activation under high-power conditions.The LN-NaF catalysts enhance CO_(2)methanation activity across the entire power range compared to LN,achieving a CO_(2)conversion of 86.3%and CH4 selectivity of 99.4%.Additionally,LN-F(h)reaches a CH4 yield 4.15 times higher than that of LN at low power.Furthermore,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy with a self-made reactor are performed under plasma-catalytic conditions to reveal the CO_(2)adsorption and conversion mechanisms,indicating that different dopants(F,Na,and NaF)exhibit promoting effects on different intermediates,resulting in variations in CO_(2)methanation activity.This study provides valuable insights for improving catalyst performance and a thorough comprehension of mechanisms in CO_(2)methanation.展开更多
Oxidative magnetization has attracted great attention as an efficient strategy for modulating physiochemical properties of magnetic biochar.In this paper,a K_(2)FeO_(4)-involving hydrothermal oxidative magnetization w...Oxidative magnetization has attracted great attention as an efficient strategy for modulating physiochemical properties of magnetic biochar.In this paper,a K_(2)FeO_(4)-involving hydrothermal oxidative magnetization was explored to regulate multiple micro-structures for manufacture magnetic hydrochar(MHC)for Fenton-like degradation of tetracycline in aqueous solution.Diverse shapes of Fe_(3)O_(4) and nano zero-valent iron(nZVI)were doped with abundant oxygen containing groups and persistent free radicals(PFRs).Multiple catalysis sites including iron species,PFRs,oxygen containing groups,and graphite defects contributed to accelerate the Fenton-like degradation with synergistic effect.Notably,MHC achieved a tetracycline removal rate of 99% within 60 min at 50 mg/L,with a total organic carbon(TOC)removal rate of 35%.Furthermore,after four cycles of reuse,the degradation efficiency slightly decreased to 93%.This study highlights the potential of magnetic hydrochar with multiple catalytic sites in the effective and sustainable degradation of pollutants.展开更多
Efficient photocatalytic reduction of CO_(2)is crucial to decrease the atmospheric concentration of CO_(2).Pairing this process with H_(2)O_(2)production is of considerable importance for simultaneously producing valu...Efficient photocatalytic reduction of CO_(2)is crucial to decrease the atmospheric concentration of CO_(2).Pairing this process with H_(2)O_(2)production is of considerable importance for simultaneously producing value-added chemicals.However,the photocatalysts reported for such a process suffer from a high recombination rate of the surface/bulk charges,as well as inefficient enrichment and activation toward CO_(2)and O_(2),resulting in low conversion efficiency even in the presence of organic sacrificial agents and expensive metal co-catalysts.Herein,two 1,3,5-triphenylbenzene-based organic polymers with high ionic density and porosity are prepared through a facile Sonogashira polymerization.The ionic imidazolium sites embedded in the polymeric skeleton provide the two polymers(iCMP-1 and iCMP-2)with adsorptive selectivity for CO_(2)/N_(2) up to 98-102 at 273 K,facilitating the enrichment of CO_(2)and O_(2)molecules around the catalytic centers,thus boosting their catalytic conversion directly from air under solar light(100 mW cm^(-2)).Benefiting from the improved charge separation and broad light absorption,along with high CO_(2)and O_(2)uptake,iCMP-2 can deliver excellent CO and H_(2)O_(2)yields(611.8 and 810.6μmol h^(-1)g^(-1),respectively)under an atmosphere composed of water vapor and air without any co-catalysts.展开更多
Accurate assessment of site quality in coastal Casuarina equisetifolia(C.equisetifolia)plantations is essential for enhancing the protective function of shelterbelts and implementing site-specific afforestation strate...Accurate assessment of site quality in coastal Casuarina equisetifolia(C.equisetifolia)plantations is essential for enhancing the protective function of shelterbelts and implementing site-specific afforestation strategies.However,traditional ground-based surveys are limited in spatial coverage and efficiency,hindering effective forest management.To overcome these limitations,this study developed an integrated assessment framework that couples ground-based modeling with remote sensing inversion to achieve large-scale site quality mapping.Field investigations on Pingtan Island,Fujian Province,China,were used to establish a ground-based evaluation model.Soil fertility was quantified using Principal Component Analysis(PCA),and principal components were classified into discrete fertility grades through K-means clustering.These grades,together with topographic variables,were incorporated into a site quality classification model constructed using Quantification Theory I.The point-based model was subsequently extrapolated using Landsat 9 imagery to generate a spatially continuous site quality map.Spatial autocorrelation(Moran’s Ⅰ)and LISA clustering were further employed to interpret spatial patterns.Results indicate that coastal sandy soils in the study area are generally nutrient-poor,with tree growth primarily constrained by total nitrogen,organic matter,available phosphorus,and total phosphorus.The five most influential site factors,ranked by importance,are soil fertility,distance from the coastline,aspect,slope gradient,and elevation.Optimal conditions for C.equisetifolia growth include fertile soil,location>1000 m from the coastline,south-facing or semi-sunny slopes,slope gradients<15°,and elevations between 10-100 m.Only 11.94%of the area was classified as high-quality(Grade I),while 61.74%fell into moderate or poor grades(Grades Ⅲ and Ⅳ),indicating that most plantations are located on suboptimal sites.This study provides scientific support for improving the precision and sustainability of coastal shelterbelt planning and management,offering practical insights for afforestation strategies,forest restoration,and ecological forestry development in coastal zones.展开更多
With increasing global energy demand and growing concerns over climate change,methods for catalytic reduction of CO_(2)have been extensively studied,among which graphitic carbon nitride(g-C_(3)N_(4))attracts remarkabl...With increasing global energy demand and growing concerns over climate change,methods for catalytic reduction of CO_(2)have been extensively studied,among which graphitic carbon nitride(g-C_(3)N_(4))attracts remarkable attention due to its easily available raw materials and outstanding chemical stability.However,its wide bandgap and low photon usage efficiency limit its application in photocatalysis.Doping g-C_(3)N_(4)to introduce active sites can enhance its catalytic performance.Herein,asymmetric phosphorus-cobalt dual sites were introduced onto g-C_(3)N_(4)via hydrothermal treatment and thermal polymerization.P(phosphorus)could enhance CO_(2)adsorption,while Co(cobalt)functions as a metallic site to boost the separation rate of photogenerated carriers.A photocatalytic CO_(2)reduction to CO with a rate of 93.2μmol/(g·h)was achieved,which was two times that of g-C_(3)N_(4).During stability testing,ethylene with a formation rate of approximately 2μmol/(g·h)was observed,as well as trace quantities of methanol and acetic acid in the liquid products.This work shows a promising strategy by the introduction of asymmetric phosphorous-cobalt dual sites for efficient photocatalytic conversion of CO_(2)to CO and C2 products.展开更多
This research aimed to obtain accurate estimates of the productivity of eucalyptus plantations under different climate change scenarios without the need for additional fieldwork.Thus,we used tree growth data from 1,10...This research aimed to obtain accurate estimates of the productivity of eucalyptus plantations under different climate change scenarios without the need for additional fieldwork.Thus,we used tree growth data from 1,102research plots,existing spatially continuous environmental data,and the random forest(RF) algorithm to construct raster-based models.We constructed models to predict site index(SI) at landscape scale(250m·pixel^(-1)),which is useful for planning purposes and for analyzing the effect of climate change on productivity,and at forest plot scale(resolutions of 10,25,50,and 100 m-pixel^(-1)),which is essential for predicting plantation yields.All models explained~50% of site index variability,as is usual in this type of study.We found that the different spatial resolutions of predictor variables did not affect the amount of variability explained.This finding may be due to two opposing effects on the explained variability at finer scales:a positive effect,as finer scales enable capture of microscale landform variability through a high-resolution digital elevation model(DEM),and a negative effect due to the introduction of "noise" when downscaling the climatic and lithological information from coarser scales.Elevation and the climatic variables(mainly temperature) were the most important predictor variables:For every 100 m-increase in elevation,the productivity decreased by on average 0.3-0.9 m of site index(1-1.3 m^(3)·ha^(-1)·year^(-1) of maximum mean annual increment in volume) and for each degree-Celsiusincrease in annual mean temperature,productivity increased by about 2.2 m in site index(3 m^(3)·ha^(-1)·year^(-1)of maximum mean annual increment in volume).Due to the forecasted increase in temperatures under climate change,productivity is expected to increase significantly in Eucalyptus globulus plantations in northern Spain in the coming decades,by between 1.68% and 3.38% of the current average site index under the most pessimistic climate change scenario and between 1.79% and 2.48% of the current average site index for the moderate scenario.We conclude that currently available spatially continuous environmental data can be used to develop accurate raster data models for predicting site productivity for E.globulus without the need for fieldwork.The spatially explicit maps produced in the study provide support to forest planners,forest managers,private landowners and politicians,enabling well-founded decisions to be made regarding selection of the best sites for afforestation and providing accurate yield predictions for the plantations.展开更多
It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for elec...It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for electrocatalytic HMF oxidative reaction(e-HMFOR)have been facing low Faradaic efficiency(FE)and high water splitting voltage.Herein,we propose a strategy of the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction by constructing a Co-Ni paired site,where the Co site is in charge of adsorbing for HMF while the electrons are transferred to the Ni site,thus giving the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction superior electrocata lytic performances for e-HMFOR and water splitting.By optimizing conditions,the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction has high conversion of 99.7%,high selectivity of 99.9%,and high FE of 98.4%at 1.3 V,as well as low cell voltage of 1.31 V at 10 mA cm^(-2)in 1 M KOH+0.1 M HMF.This study offers a potential insight for e-HMFOR to high value-added FDCA coupling water splitting to produce H_(2)in an economical manner.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
The CO_(2)-assisted oxidative dehydrogenation of ethane(CO_(2)-ODHE)provides a promising way to produce ethylene and utilize CO_(2).Simultaneous upgrading of ethane into the high value-added chemical products and the ...The CO_(2)-assisted oxidative dehydrogenation of ethane(CO_(2)-ODHE)provides a promising way to produce ethylene and utilize CO_(2).Simultaneous upgrading of ethane into the high value-added chemical products and the reduction of greenhouse gas CO_(2)emissions could be achieved.However,the targeted breaking of the C-C/C-H bonds of ethane is still a challenge for the designed catalysts.In this paper,ZnO-doped ZrO_(2)bifunctional catalysts(Zn_(x)ZrO)with different Zn/Zr molar ratios were prepared by the deposition-precipitation method,and the functions of various sites for CO_(2)-ODHE reaction were revealed by in situ characterizations and ethane pulse experiment:the medium-strength acidic Zn-O-Zr sites are responsible for the purposefully cracking of ethane C-H bonds to ethylene,while the more oxygen vacancies(OV)created by the introduction of Zn^(2+)are responsible for the efficient activation C=O bonds of CO_(2),thus promoting the RWGS reaction.In addition,the Zn0.2ZrO catalyst demonstrated excellent catalytic performances,with C_(2)H_(6)conversion,C_(2)H_(4)yield,and CO_(2)conversion about 19.1%,10.5%,and 10.6%within 5 h,respectively(600℃,GHSV=3000 mL/(g·h)).Especially,the initial ethylene space-time yield of 355.5μmol/(min·g)was obtained under 6000 mL/(g·h);Finally,the tandem reaction mechanism of ethane dehydrogenation and RWGS was revealed.展开更多
Addressing the complex issue of emergency resource distribution center site selection in uncertain environments, this study was conducted to comprehensively consider factors such as uncertainty parameters and the urge...Addressing the complex issue of emergency resource distribution center site selection in uncertain environments, this study was conducted to comprehensively consider factors such as uncertainty parameters and the urgency of demand at disaster-affected sites. Firstly, urgency cost, economic cost, and transportation distance cost were identified as key objectives. The study applied fuzzy theory integration to construct a triangular fuzzy multi-objective site selection decision model. Next, the defuzzification theory transformed the fuzzy decision model into a precise one. Subsequently, an improved Chaotic Quantum Multi-Objective Harris Hawks Optimization (CQ-MOHHO) algorithm was proposed to solve the model. The CQ-MOHHO algorithm was shown to rapidly produce high-quality Pareto front solutions and identify optimal site selection schemes for emergency resource distribution centers through case studies. This outcome verified the feasibility and efficacy of the site selection decision model and the CQ-MOHHO algorithm. To further assess CQ-MOHHO’s performance, Zitzler-Deb-Thiele (ZDT) test functions, commonly used in multi-objective optimization, were employed. Comparisons with Multi-Objective Harris Hawks Optimization (MOHHO), Non-dominated Sorting Genetic Algorithm II (NSGA-II), and Multi-Objective Grey Wolf Optimizer (MOGWO) using Generational Distance (GD), Hypervolume (HV), and Inverted Generational Distance (IGD) metrics showed that CQ-MOHHO achieved superior global search ability, faster convergence, and higher solution quality. The CQ-MOHHO algorithm efficiently achieved a balance between multiple objectives, providing decision-makers with satisfactory solutions and a valuable reference for researching and applying emergency site selection problems.展开更多
Electrocatalytic conversion of renewable biomass is emerging as a promising route for sustainable chemical production;hence it urgently calls for developing efficient electrocatalysts with low potentials and high curr...Electrocatalytic conversion of renewable biomass is emerging as a promising route for sustainable chemical production;hence it urgently calls for developing efficient electrocatalysts with low potentials and high current densities.Herein,a Pr-doped Co(OH)_(2)hexagonal sheet(Pr/Co=1/9,in mole)is synthesized by electrodeposition as highly performant catalyst for 5-hydroxymethylfurfural(HMF)oxidation reaction(HMFOR)to produce 2,5-furandicarboxylic acid(FDCA).This novel and low-cost catalyst possesses a rather low onset potential of 1.05 V(vs.RHE)and requires only 1.10 V(vs.RHE)to reach a current density of 10 mA cm^(-2)for HMFOR,significantly outperforming Co(OH)_(2)benchmark(i.e.,210 mV higher to reach10 m A cm^(-2)).The origin of Pr promotion effect as well as the evolution of CoOOH catalytic sites and HMFOR process has been deeply elucidated by physical characterizations,kinetic experiments,in situ electrochemical techniques,and theoretical calculations.The unique Pr-ameliorated CoOOH active centers enable 100%conversion of HMF,99.6%selectivity of FDCA,and 99.7%Faraday efficiency,with a superior cycling durability toward HMFOR.This can be one of the most outstanding results for Co-based HMFOR catalysts to date in the literature.Thereby this work can help open up new horizons for constructing novel and efficient Co-based electrocatalysts by the utilization of lanthanide elements.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
Antimony smelting activities damage the soil and vegetation surroundings while generating economic value.However,no standardizedmethods are available to diagnose the extent of soil degradation at antimony smelting sit...Antimony smelting activities damage the soil and vegetation surroundings while generating economic value.However,no standardizedmethods are available to diagnose the extent of soil degradation at antimony smelting sites.This study developed a standardized framework for assessing soil quality by consideringmicrobial-induced resilience and heavymetal contamination at Xikuangshan antimony smelting site.The soil resilience index(SRI)and soil contamination index(SCI)were calculated byMinimum Data Set and geo-accumulation model,respectively.After standardized by a multi-criteria quantitative procedure of modified Nemerow’s pollution index(NPI),the integrated assessment of soil quality index(SQI),which is the minimumof SRINPI and SCINPI,was achieved.The results showed that Sb and As were the prominent metal(loid)pollutants,and significant correlations between SQI and SRI indicated that the poor soil quality was mainly caused by the low level of soil resilience.The primary limiting factors of SRI were Fungi in high andmiddle contaminated areas,and Skermanella in low contaminated area,suggesting that the weak soil resilience was caused by low specific microbial abundances.Microbial regulation and phytoremediation are greatly required to improve the soil quality at antimony smelting sites from the perspectives of pollution control and resilience improvement.This study improves our understanding of ecological effects of antimony smelting sites and provides a theoretical basis for ecological restoration and sustainable development of mining areas.展开更多
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 the National Natural Science Foundation of China(U23A20120 and 22425601)National Key R&D Program of China(2023YFB3810801)+2 种基金Natural Science Foundation of Hebei Province(B2021208033)Beijing Nova Program(20240484659)R&D Program of Beijing Municipal Education Commission(KZ202210005011).
文摘Directional catalytic transformation of volatile organic compounds(VOCs)into value-added chemicals represents a more sustainable strategy than complete mineralization,as it simultaneously mitigates environmental pollution and reduces carbon emissions.The primary challenge in achieving multifunctional olefin production from alcohol-type VOCs is the lack of mechanistic clarity,which hinders the targeted synthesis of selective catalysts.Herein,we developed W-Ti hybrid metal oxide catalysts(WTiO_(x))with active Ti-O-W interfaces via a one-step hydrothermal synthesis and demonstrated their effectiveness for isopropanol conversion processes.Remarkably,WTiO_(x)-500 achieved 99.8%isopropanol conversion and 99.3% propylene yield at 140℃,significantly outperforming TiO_(2)(98.4% yield at 180℃)and WO_(3)(90.5% yield at 240℃).WTiO_(x)-500 also displayed higher thermal stability,with isopropanol conversion and propylene yield decreasing by 1.0%and 1.6% after 35 h on-stream reaction.Although impurities(e.g.,CO_(2),HCl,SO_(2))caused partial deactivation of WTiO_(x)-500,oxygen treatment regenerated the catalyst.A series of characterization techniques indicated that the controlled calcination temperature promoted the formation of an optimal Ti-O-Winterface in WTiO_(x)-500 through W substitution into the TiO_(2)lattice and WO_(3)-TiO_(2)surface interaction,where W species effectively tuned the electronic structure.This configuration endowed WTiO_(x)-500 with moderate acidity of BrФnsted(-OH)and Lewis(Ti^(4+)/W^(6+))acid sites,which synergistically facilitated charge transfer between isopropanol and catalyst,accelerated C-O bond cleavage during dehydration.This work provides mechanistic insights into isopropanol dehydration and demonstrates a potential approach for VOC valorization.
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
基金supported by the National Natural Science Foundation of China(Nos.W2412093 and 52170068)the Fundamental Research Funds for the Central Universities(No.DUT24RC(3)079).
文摘Peroxymonosulfate(PMS)-based advanced oxidation technology has been proven to be a viable option for the decontamination of organic pollutants from water bodies.Advanced catalyst design is essential to this technology.Herein,a vanadium-doped LaFeO_(3) perovskite(LFO-V)featuring asymmetric Fe-O-V sites was rationally designed.Thanks to orbital electron interaction between Fe and V atoms,the modified electronic structure elevated electron density near the Fermi energy level while reducing the energy barrier toward effective PMS activation.This facilitated concurrent PMS reduction at the Fe sites to generate SO_(4)^(·-)and·OH(57.7%),and PMS oxidation at V sites to produce ^(1)O_(2)(42.3%).The LFO-V/PMS system demonstrated excellent tetracycline(TC)degradation performance with a 2-fold enhancement in rate constant compared to that of pristine LFO.Further,the LFO-V maintained long-term stability,and the toxicity of degradation intermediates was evaluated through microbial metabolomics.This work establishes an effective route to regulate the PMS activation pathways through precise electronic structure modulation,advancing the rational design of advanced Fenton-like catalysts.
基金supported by the National Natural Science Foundation of China(No.22278203).
文摘Seawater electrolysis has attracted considerable attention in hydrogen production.However,the chloride ions(Cl^(-))in seawater can corrode metal sites and decrease the lifespans of the oxygen evolution reaction(OER).Herein,we report a reversed-active sites strategy,converting Cl^(-)-affinitive metal sites to Cl^(-)-repellent oxygen sites,for OER in alkaline seawater electrolysis.First,ex/in situ experiments confirm the effectiveness of such a strategy using typical perovskites following the adsorbate evolution mechanism(AEM)or lattice oxygen-mediated mechanism(LOM).Furthermore,the origins of the superior activity and durability of as-prepared La_(0.3)SrCo_(0.5)Fe_(0.5)Ox(La_(0.3))can be ascribed to higher participation of lattice oxygen in OER,rapid bulk oxygen diffusion,and excellent OH-adsorption kinetics.Hence,an alkaline seawater electrolytic cell with La_(0.3)as the anode produces 10 mA cm^(-2)at just 1.57 V and maintains near-constant activity over 150 hours.This work introduces novel concepts for the production of superactive and steady electrocatalysts for the electrolysis of seawater.
基金supported by the National Natural Science Foundation of China(No.51878292).
文摘Large-scale CO_(2)emissions have exacerbated the greenhouse effect,reinforcing the critical need for efficient CO_(2)mitigation methods.Plasma-catalytic technology enables CO_(2)conversion under mild conditions,especially for CO_(2)methanation(the Sabatier reaction),which has attracted significant attention due to its economic benefits and the potential for safe energy transportation via existing natural gas pipelines.The development of high-performance CO_(2)methanation catalysts remains an ongoing and long-term objective,and there is a lack of adequate in-situ characterization techniques to investigate the mechanisms.This study focuses on the Ni/La_(2)O_(3)(LN)catalyst and introduces two CO_(2)activation strategies through F and Na modifications:the Ni-Ov-Ni site activation with electron transfer from Ni0 under low-power conditions and basic site activation under high-power conditions.The LN-NaF catalysts enhance CO_(2)methanation activity across the entire power range compared to LN,achieving a CO_(2)conversion of 86.3%and CH4 selectivity of 99.4%.Additionally,LN-F(h)reaches a CH4 yield 4.15 times higher than that of LN at low power.Furthermore,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy with a self-made reactor are performed under plasma-catalytic conditions to reveal the CO_(2)adsorption and conversion mechanisms,indicating that different dopants(F,Na,and NaF)exhibit promoting effects on different intermediates,resulting in variations in CO_(2)methanation activity.This study provides valuable insights for improving catalyst performance and a thorough comprehension of mechanisms in CO_(2)methanation.
基金supported byHainan Provincial Natural Science Foundation of China(Nos.422RC600,519QN175)National Natural Science Foundation ofChina(Nos.52160018,21801053,52400206,52500209)High-Level Talent Program of Hainan Province(Nos.XJ2400008202,XJ2400011473).
文摘Oxidative magnetization has attracted great attention as an efficient strategy for modulating physiochemical properties of magnetic biochar.In this paper,a K_(2)FeO_(4)-involving hydrothermal oxidative magnetization was explored to regulate multiple micro-structures for manufacture magnetic hydrochar(MHC)for Fenton-like degradation of tetracycline in aqueous solution.Diverse shapes of Fe_(3)O_(4) and nano zero-valent iron(nZVI)were doped with abundant oxygen containing groups and persistent free radicals(PFRs).Multiple catalysis sites including iron species,PFRs,oxygen containing groups,and graphite defects contributed to accelerate the Fenton-like degradation with synergistic effect.Notably,MHC achieved a tetracycline removal rate of 99% within 60 min at 50 mg/L,with a total organic carbon(TOC)removal rate of 35%.Furthermore,after four cycles of reuse,the degradation efficiency slightly decreased to 93%.This study highlights the potential of magnetic hydrochar with multiple catalytic sites in the effective and sustainable degradation of pollutants.
基金supported by the Excellent Youth Foundation of Jiangxi Scientific Committee(no.20232ACB213012)National Science Foundation of Jiangxi Province of China(no.20242BAB25236)+2 种基金Jiangxi Talent Program(no.DHSQT32022005)Beijing Institute of Technology Research Fund Program for Young Scholars(XSQD-202215006)National Natural Science Foundation of China(no.22202008 and 22202039).
文摘Efficient photocatalytic reduction of CO_(2)is crucial to decrease the atmospheric concentration of CO_(2).Pairing this process with H_(2)O_(2)production is of considerable importance for simultaneously producing value-added chemicals.However,the photocatalysts reported for such a process suffer from a high recombination rate of the surface/bulk charges,as well as inefficient enrichment and activation toward CO_(2)and O_(2),resulting in low conversion efficiency even in the presence of organic sacrificial agents and expensive metal co-catalysts.Herein,two 1,3,5-triphenylbenzene-based organic polymers with high ionic density and porosity are prepared through a facile Sonogashira polymerization.The ionic imidazolium sites embedded in the polymeric skeleton provide the two polymers(iCMP-1 and iCMP-2)with adsorptive selectivity for CO_(2)/N_(2) up to 98-102 at 273 K,facilitating the enrichment of CO_(2)and O_(2)molecules around the catalytic centers,thus boosting their catalytic conversion directly from air under solar light(100 mW cm^(-2)).Benefiting from the improved charge separation and broad light absorption,along with high CO_(2)and O_(2)uptake,iCMP-2 can deliver excellent CO and H_(2)O_(2)yields(611.8 and 810.6μmol h^(-1)g^(-1),respectively)under an atmosphere composed of water vapor and air without any co-catalysts.
基金supported by University Key Lab for Geomatics Technology&Optimize Resources Utilization in Fujian Province(KJG20104A)Fujian Forestry Science and Technology project(2023FKJ15)Fuzhou Forestry Science and Technology Research Project(2130206).
文摘Accurate assessment of site quality in coastal Casuarina equisetifolia(C.equisetifolia)plantations is essential for enhancing the protective function of shelterbelts and implementing site-specific afforestation strategies.However,traditional ground-based surveys are limited in spatial coverage and efficiency,hindering effective forest management.To overcome these limitations,this study developed an integrated assessment framework that couples ground-based modeling with remote sensing inversion to achieve large-scale site quality mapping.Field investigations on Pingtan Island,Fujian Province,China,were used to establish a ground-based evaluation model.Soil fertility was quantified using Principal Component Analysis(PCA),and principal components were classified into discrete fertility grades through K-means clustering.These grades,together with topographic variables,were incorporated into a site quality classification model constructed using Quantification Theory I.The point-based model was subsequently extrapolated using Landsat 9 imagery to generate a spatially continuous site quality map.Spatial autocorrelation(Moran’s Ⅰ)and LISA clustering were further employed to interpret spatial patterns.Results indicate that coastal sandy soils in the study area are generally nutrient-poor,with tree growth primarily constrained by total nitrogen,organic matter,available phosphorus,and total phosphorus.The five most influential site factors,ranked by importance,are soil fertility,distance from the coastline,aspect,slope gradient,and elevation.Optimal conditions for C.equisetifolia growth include fertile soil,location>1000 m from the coastline,south-facing or semi-sunny slopes,slope gradients<15°,and elevations between 10-100 m.Only 11.94%of the area was classified as high-quality(Grade I),while 61.74%fell into moderate or poor grades(Grades Ⅲ and Ⅳ),indicating that most plantations are located on suboptimal sites.This study provides scientific support for improving the precision and sustainability of coastal shelterbelt planning and management,offering practical insights for afforestation strategies,forest restoration,and ecological forestry development in coastal zones.
基金supported financially by National Natural Science Foundation of China(No.52302226)the start-up Research Found of Southeast University(Nos.RF1028623127 and RF1028623128)the Natural Science Foundation of Jiangsu Province(No.BK20230812).
文摘With increasing global energy demand and growing concerns over climate change,methods for catalytic reduction of CO_(2)have been extensively studied,among which graphitic carbon nitride(g-C_(3)N_(4))attracts remarkable attention due to its easily available raw materials and outstanding chemical stability.However,its wide bandgap and low photon usage efficiency limit its application in photocatalysis.Doping g-C_(3)N_(4)to introduce active sites can enhance its catalytic performance.Herein,asymmetric phosphorus-cobalt dual sites were introduced onto g-C_(3)N_(4)via hydrothermal treatment and thermal polymerization.P(phosphorus)could enhance CO_(2)adsorption,while Co(cobalt)functions as a metallic site to boost the separation rate of photogenerated carriers.A photocatalytic CO_(2)reduction to CO with a rate of 93.2μmol/(g·h)was achieved,which was two times that of g-C_(3)N_(4).During stability testing,ethylene with a formation rate of approximately 2μmol/(g·h)was observed,as well as trace quantities of methanol and acetic acid in the liquid products.This work shows a promising strategy by the introduction of asymmetric phosphorous-cobalt dual sites for efficient photocatalytic conversion of CO_(2)to CO and C2 products.
基金supported by the research project of code PID2020-112839RB-I00 funded by the Spanish State Research Agency(AEI)of the Ministry of Science and Innovation(MCIN/AEI/10.13039/501100011033)in receipt of a Severo Ochoa Fellowship from the Asturias Government(code BP21-125).
文摘This research aimed to obtain accurate estimates of the productivity of eucalyptus plantations under different climate change scenarios without the need for additional fieldwork.Thus,we used tree growth data from 1,102research plots,existing spatially continuous environmental data,and the random forest(RF) algorithm to construct raster-based models.We constructed models to predict site index(SI) at landscape scale(250m·pixel^(-1)),which is useful for planning purposes and for analyzing the effect of climate change on productivity,and at forest plot scale(resolutions of 10,25,50,and 100 m-pixel^(-1)),which is essential for predicting plantation yields.All models explained~50% of site index variability,as is usual in this type of study.We found that the different spatial resolutions of predictor variables did not affect the amount of variability explained.This finding may be due to two opposing effects on the explained variability at finer scales:a positive effect,as finer scales enable capture of microscale landform variability through a high-resolution digital elevation model(DEM),and a negative effect due to the introduction of "noise" when downscaling the climatic and lithological information from coarser scales.Elevation and the climatic variables(mainly temperature) were the most important predictor variables:For every 100 m-increase in elevation,the productivity decreased by on average 0.3-0.9 m of site index(1-1.3 m^(3)·ha^(-1)·year^(-1) of maximum mean annual increment in volume) and for each degree-Celsiusincrease in annual mean temperature,productivity increased by about 2.2 m in site index(3 m^(3)·ha^(-1)·year^(-1)of maximum mean annual increment in volume).Due to the forecasted increase in temperatures under climate change,productivity is expected to increase significantly in Eucalyptus globulus plantations in northern Spain in the coming decades,by between 1.68% and 3.38% of the current average site index under the most pessimistic climate change scenario and between 1.79% and 2.48% of the current average site index for the moderate scenario.We conclude that currently available spatially continuous environmental data can be used to develop accurate raster data models for predicting site productivity for E.globulus without the need for fieldwork.The spatially explicit maps produced in the study provide support to forest planners,forest managers,private landowners and politicians,enabling well-founded decisions to be made regarding selection of the best sites for afforestation and providing accurate yield predictions for the plantations.
基金supported by the National Natural Science Foundation of China(22302019)the Changzhou Sci&Tech Program(CJ20220214).
文摘It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for electrocatalytic HMF oxidative reaction(e-HMFOR)have been facing low Faradaic efficiency(FE)and high water splitting voltage.Herein,we propose a strategy of the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction by constructing a Co-Ni paired site,where the Co site is in charge of adsorbing for HMF while the electrons are transferred to the Ni site,thus giving the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction superior electrocata lytic performances for e-HMFOR and water splitting.By optimizing conditions,the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction has high conversion of 99.7%,high selectivity of 99.9%,and high FE of 98.4%at 1.3 V,as well as low cell voltage of 1.31 V at 10 mA cm^(-2)in 1 M KOH+0.1 M HMF.This study offers a potential insight for e-HMFOR to high value-added FDCA coupling water splitting to produce H_(2)in an economical manner.
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.
文摘The CO_(2)-assisted oxidative dehydrogenation of ethane(CO_(2)-ODHE)provides a promising way to produce ethylene and utilize CO_(2).Simultaneous upgrading of ethane into the high value-added chemical products and the reduction of greenhouse gas CO_(2)emissions could be achieved.However,the targeted breaking of the C-C/C-H bonds of ethane is still a challenge for the designed catalysts.In this paper,ZnO-doped ZrO_(2)bifunctional catalysts(Zn_(x)ZrO)with different Zn/Zr molar ratios were prepared by the deposition-precipitation method,and the functions of various sites for CO_(2)-ODHE reaction were revealed by in situ characterizations and ethane pulse experiment:the medium-strength acidic Zn-O-Zr sites are responsible for the purposefully cracking of ethane C-H bonds to ethylene,while the more oxygen vacancies(OV)created by the introduction of Zn^(2+)are responsible for the efficient activation C=O bonds of CO_(2),thus promoting the RWGS reaction.In addition,the Zn0.2ZrO catalyst demonstrated excellent catalytic performances,with C_(2)H_(6)conversion,C_(2)H_(4)yield,and CO_(2)conversion about 19.1%,10.5%,and 10.6%within 5 h,respectively(600℃,GHSV=3000 mL/(g·h)).Especially,the initial ethylene space-time yield of 355.5μmol/(min·g)was obtained under 6000 mL/(g·h);Finally,the tandem reaction mechanism of ethane dehydrogenation and RWGS was revealed.
文摘Addressing the complex issue of emergency resource distribution center site selection in uncertain environments, this study was conducted to comprehensively consider factors such as uncertainty parameters and the urgency of demand at disaster-affected sites. Firstly, urgency cost, economic cost, and transportation distance cost were identified as key objectives. The study applied fuzzy theory integration to construct a triangular fuzzy multi-objective site selection decision model. Next, the defuzzification theory transformed the fuzzy decision model into a precise one. Subsequently, an improved Chaotic Quantum Multi-Objective Harris Hawks Optimization (CQ-MOHHO) algorithm was proposed to solve the model. The CQ-MOHHO algorithm was shown to rapidly produce high-quality Pareto front solutions and identify optimal site selection schemes for emergency resource distribution centers through case studies. This outcome verified the feasibility and efficacy of the site selection decision model and the CQ-MOHHO algorithm. To further assess CQ-MOHHO’s performance, Zitzler-Deb-Thiele (ZDT) test functions, commonly used in multi-objective optimization, were employed. Comparisons with Multi-Objective Harris Hawks Optimization (MOHHO), Non-dominated Sorting Genetic Algorithm II (NSGA-II), and Multi-Objective Grey Wolf Optimizer (MOGWO) using Generational Distance (GD), Hypervolume (HV), and Inverted Generational Distance (IGD) metrics showed that CQ-MOHHO achieved superior global search ability, faster convergence, and higher solution quality. The CQ-MOHHO algorithm efficiently achieved a balance between multiple objectives, providing decision-makers with satisfactory solutions and a valuable reference for researching and applying emergency site selection problems.
基金National Natural Science Foundation of China(No.22272149,22062025)Yunnan University’s Research Innovation Fund for Graduate Students(No.KC-23234085)+1 种基金Workstation of Academician Chen Jing of Yunnan Province(No.202105AF150012)Free Exploration Fund for Academician(No.202405AA350001)。
文摘Electrocatalytic conversion of renewable biomass is emerging as a promising route for sustainable chemical production;hence it urgently calls for developing efficient electrocatalysts with low potentials and high current densities.Herein,a Pr-doped Co(OH)_(2)hexagonal sheet(Pr/Co=1/9,in mole)is synthesized by electrodeposition as highly performant catalyst for 5-hydroxymethylfurfural(HMF)oxidation reaction(HMFOR)to produce 2,5-furandicarboxylic acid(FDCA).This novel and low-cost catalyst possesses a rather low onset potential of 1.05 V(vs.RHE)and requires only 1.10 V(vs.RHE)to reach a current density of 10 mA cm^(-2)for HMFOR,significantly outperforming Co(OH)_(2)benchmark(i.e.,210 mV higher to reach10 m A cm^(-2)).The origin of Pr promotion effect as well as the evolution of CoOOH catalytic sites and HMFOR process has been deeply elucidated by physical characterizations,kinetic experiments,in situ electrochemical techniques,and theoretical calculations.The unique Pr-ameliorated CoOOH active centers enable 100%conversion of HMF,99.6%selectivity of FDCA,and 99.7%Faraday efficiency,with a superior cycling durability toward HMFOR.This can be one of the most outstanding results for Co-based HMFOR catalysts to date in the literature.Thereby this work can help open up new horizons for constructing novel and efficient Co-based electrocatalysts by the utilization of lanthanide elements.
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 National Key Research and Development Program of China (No.2019YFC1803604)the National Natural Science Foundation of China (Nos.42007306 and 42277193).
文摘Antimony smelting activities damage the soil and vegetation surroundings while generating economic value.However,no standardizedmethods are available to diagnose the extent of soil degradation at antimony smelting sites.This study developed a standardized framework for assessing soil quality by consideringmicrobial-induced resilience and heavymetal contamination at Xikuangshan antimony smelting site.The soil resilience index(SRI)and soil contamination index(SCI)were calculated byMinimum Data Set and geo-accumulation model,respectively.After standardized by a multi-criteria quantitative procedure of modified Nemerow’s pollution index(NPI),the integrated assessment of soil quality index(SQI),which is the minimumof SRINPI and SCINPI,was achieved.The results showed that Sb and As were the prominent metal(loid)pollutants,and significant correlations between SQI and SRI indicated that the poor soil quality was mainly caused by the low level of soil resilience.The primary limiting factors of SRI were Fungi in high andmiddle contaminated areas,and Skermanella in low contaminated area,suggesting that the weak soil resilience was caused by low specific microbial abundances.Microbial regulation and phytoremediation are greatly required to improve the soil quality at antimony smelting sites from the perspectives of pollution control and resilience improvement.This study improves our understanding of ecological effects of antimony smelting sites and provides a theoretical basis for ecological restoration and sustainable development of mining areas.
