Large-scale deployment of carbon dioxide(CO_(2))removal technology is an essential step to cope with global warming and achieve carbon neutrality.Direct air capture(DAC)has recently received increasing attention given...Large-scale deployment of carbon dioxide(CO_(2))removal technology is an essential step to cope with global warming and achieve carbon neutrality.Direct air capture(DAC)has recently received increasing attention given the high flexibility to remove CO_(2)from discrete sources.Porous materials with adjustable pore characteristics are promising sorbents with low or no latent heat of vaporization.This review article has summarized the recent development of porous sorbents for DAC,with a focus of pore engineering strategy and adsorption mechanism.Physisorbents such as zeolites,porous carbons,metal-organic frameworks(MOFs),and amine-modified chemisorbents have been discussed and their challenges in practical application have been analyzed.At last,future directions have been proposed,and it is expected to inspire collaborations from chemistry,environment,material science and engineering communities.展开更多
In this work,we developed plasmonic photocatalyst composed of Cu Pd alloy nanoparticles supported on Ti N,the optimized Cu_(3)Pd_(2)/Ti N catalyst shows excellent conversion(>96%)and selectivity(>99%)for Heck re...In this work,we developed plasmonic photocatalyst composed of Cu Pd alloy nanoparticles supported on Ti N,the optimized Cu_(3)Pd_(2)/Ti N catalyst shows excellent conversion(>96%)and selectivity(>99%)for Heck reaction at 50℃ under visible light irradiation.By in-situ spectroscopic investigations,we find that visible light excitation could achieve stable metallic Cu species on the surface of Cu Pd alloy nanoparticles,thereby eliminating the inevitable surface oxides of Cu based catalyst.The in-situ formed metallic Cu species under irradiation take advantage of the strong interactions of Cu with visible light,and manifest in the localized surface plasmon resonances(LSPR)photoexcitation.Visible light excitation could further promote the charge transfer between catalytic Pd component and the support Ti N,resulting in electron-rich Pd sites on Cu Pd/Ti N.Moreover,light excitation on Cu Pd/Ti N generates strong chemisorption of iodobenzene and styrene,favoring the activation of reactants for Heck reaction.DFT calculations suggest that electron-rich Cu Pd sites ideally lower the activation energy barrier for the coupling reaction.This work provides valuable insights for mechanistic understanding of plasmonic photocatalysis.展开更多
In this study,six-dimensional(6D)time-dependent wave packet calcula-tions were employed to investigate the dissociation of HCl molecules on two bimetallic surfaces,Cu/Ag(111)and Cu/Au(111).These calculations were base...In this study,six-dimensional(6D)time-dependent wave packet calcula-tions were employed to investigate the dissociation of HCl molecules on two bimetallic surfaces,Cu/Ag(111)and Cu/Au(111).These calculations were based on two accurate potential energy surfaces(PESs)constructed using neu-ral network methodology.Density functional theory(DFT)calculations revealed that the static barrier heights for HCl on Cu/Ag(111)and Cu/Au(111)were 0.32 eV and 0.28 eV,respectively.These values are significantly lower than the barrier height on pure Cu(111)(0.52 eV),primarily due to surface strain effects.However,it was found that the 6D dissociation probability of HCl in(v=0,1,j=0)states on Cu/Au(111)was considerably lower,despite its barrier height being 0.04 eV lower than that for Cu/Ag(111).The underlying mechanism for this observation was attributed to the non-monotonic dependence of the minimum energy path(MEP)on the molecular orientation,which was induced by charge transfer effect for HCl+Cu/Au(111).In contrast,HCl+Cu/Ag(111)exhibited a monotonic dependence.These contrasting behaviors led to dis-tinct differences in rotational alignment and excitation effects for the two reactions.展开更多
Electrocatalysis has been extensively explored for the storage and conversion of renewable electric power.Understanding the physisorption and chemisorption processes at electrified solid–liquid interfaces(ESLIs)is cr...Electrocatalysis has been extensively explored for the storage and conversion of renewable electric power.Understanding the physisorption and chemisorption processes at electrified solid–liquid interfaces(ESLIs)is crucial for revealing the typical surface restructuring and catalyst dissolution during electrocatalysis.Although advanced in situ tools and theoretical models have been proposed[1,2],identifying the nature of the active sites with atomic-scale spatial resolution remains a challenge,especially at ESLIs.In a recent work published in Nature,Zhang et al.[3]reported a groundbreaking atomic-resolution imaging of the structural dynamics of Cu nanowire catalysts in ESLIs for electrochemical CO_(2)reduction(ECR).展开更多
Carbon capture and storage(CCS)is an advanced environmental technology for mitigating CO_(2) emissions and addressing climate change.Among the various approaches,adsorption has emerged as a promising method for CO_(2)...Carbon capture and storage(CCS)is an advanced environmental technology for mitigating CO_(2) emissions and addressing climate change.Among the various approaches,adsorption has emerged as a promising method for CO_(2) capture due to its effiectiveness and practicality.This review explores the potential of clay minerals as adsorbents for CO_(2) capture,providing an in-depth analysis of their inherent properties and the mechanisms involved in adsorption process.The review begins with an introduction to CCS and the concept of adsorption,followed by a detailed examination of various clay minerals,including sepiolite,montmorillonite,bentonite,kaolinite,saponite,halloysite,and illite.Each mineral’s suitability for CO_(2) adsorption is assessed,highlighting the specific properties that contribute to their performance.The mechanisms of CO_(2) adsorption including physisorption,chemisorption,ion exchange,pore diffusion,intraparticle diffusion,surface complexation,and competitive adsorption are thoroughly discussed.The review also covers the modification of clay minerals through physical and chemical treatments,amine functionalization,and composite formation to enhance their CO_(2) adsorption capacity.Additionally,regeneration methods such as temperature-swing adsorption(TSA),pressure-swing adsorption(PSA),and purging are discussed,along with CO_(2) recovery and storage techniques for improving energy efficiency.The review concludes with an overview of characterization methods for clay-based adsorbents and potential applications,while addressing the challenges and future trends in thefield.This work emphasizes the promising role of clay-based adsorbents in advancing CCS technology.展开更多
Li_(6)ZnO_(4)was chemically modified by nickel addition,in order to develop different compositions of the solid solution Li_(6)Zn_(1-x)Ni_(x)O_(4).These materials were evaluated bifunctionally;analyzing their CO_(2)ca...Li_(6)ZnO_(4)was chemically modified by nickel addition,in order to develop different compositions of the solid solution Li_(6)Zn_(1-x)Ni_(x)O_(4).These materials were evaluated bifunctionally;analyzing their CO_(2)capture performances,aswell as on their catalytic properties for H_(2)production via dry reforming of methane(DRM).The crystal structures of Li_(6)Zn_(1-x)Ni_(x)O_(4)solid solution samples were determined through X-ray diffraction,which confirmed the integration of nickel ions up to a concentration around 20 mol%,meanwhile beyond this value,a secondary phase was detected.These results were supported by XPS and TEM analyses.Then,dynamic and isothermal thermogravimetric analyses of CO_(2)capture revealed that Li_(6)Zn_(1-x)Ni_(x)O_(4)solid solution samples exhibited good CO_(2)chemisorption efficiencies,similarly to the pristine Li_(6)ZnO_(4)chemisorption trends observed.Moreover,a kinetic analysis of CO_(2)isothermal chemisorptions,using the Avrami-Erofeev model,evidenced an increment of the constant rates as a function of the Ni content.Since Ni^(2+)ions incorporation did not reduce the CO_(2)capture efficiency and kinetics,the catalytic properties of thesematerialswere evaluated in the DRM process.Results demonstrated that nickel ions favored hydrogen(H_(2))production over the pristine Li_(6)ZnO_(4)phase,despite a second H2 production reaction was determined,methane decomposition.Thereby,Li_(6)Zn_(1-x)Ni_(x)O_(4)ceramics can be employed as bifunctional materials.展开更多
Heterogeneous catalysis remains at the core of various bulk chemical manufacturing and energy conversion processes,and its revolution necessitates the hunt for new materials with ideal catalytic activities and economi...Heterogeneous catalysis remains at the core of various bulk chemical manufacturing and energy conversion processes,and its revolution necessitates the hunt for new materials with ideal catalytic activities and economic feasibility.Computational high-throughput screening presents a viable solution to this challenge,as machine learning(ML)has demonstrated its great potential in accelerating such processes by providing satisfactory estimations of surface reactivity with relatively low-cost information.This review focuses on recent progress in applying ML in adsorption energy prediction,which predominantly quantifies the catalytic potential of a solid catalyst.ML models that leverage inputs from different categories and exhibit various levels of complexity are classified and discussed.At the end of the review,an outlook on the current challenges and future opportunities of ML-assisted catalyst screening is supplied.We believe that this review summarizes major achievements in accelerating catalyst discovery through ML and can inspire researchers to further devise novel strategies to accelerate materials design and,ultimately,reshape the chemical industry and energy landscape.展开更多
Lithium-sulfur batteries(LSBs)with high energy densities have been demonstrated the potential for energy-intensive demand applications.However,their commercial applicability is hampered by hysteretic electrode reactio...Lithium-sulfur batteries(LSBs)with high energy densities have been demonstrated the potential for energy-intensive demand applications.However,their commercial applicability is hampered by hysteretic electrode reaction kinetics and the shuttle effect of lithium polysulfides(LiPSs).In this work,an interlayer consisting of high-entropy metal oxide(Cu_(0.7)Fe_(0.6)Mn_(0.4)Ni_(0.6)Sn_(0.5))O_(4) grown on carbon nanofibers(HEO/CNFs)is designed for LSBs.The CNFs with highly porous networks provide transport pathways for Li^(+) and e^(-),as well as a physical sieve effect to limit LiPSs crossover.In particular,the grapevine-like HEO nanoparticles generate metal-sulfur bonds with LiPSs,efficiently anchoring active materials.The unique structure and function of the interlayer enable the LSBs with superior electrochemical performance,i.e.,the high specific capacity of 1381 mAh g^(-1) at 0.1 C and 561 mAh g^(-1) at 6 C.This work presents a facile strategy for exploiting high-performance LSBs.展开更多
The adsorption of sodium oleate(NaOL)at the microfine hematite/aqueous solution interface was investigated in this paper.Experimental research indicated that negative effects stemmed from the dissolution of the microf...The adsorption of sodium oleate(NaOL)at the microfine hematite/aqueous solution interface was investigated in this paper.Experimental research indicated that negative effects stemmed from the dissolution of the microfine hematite(D50=19.21μm)could be effectively eliminated via the appropriate dosage of NaOL at alkali pH conditions.Solution chemistry calculation and adsorption test results indicated that RCOOand(RCOO)_(2)^(2-) ions were responsible for microfine hematite flotation at pH 8.2.Zeta potential and FTIR measurements confirmed the co-adsorption of molecular and ionic oleate species occurred at pH 8.2.X-ray photoelectron spectroscopy(XPS)results further indicated that oleate species interacted with hematite surfaces mainly through chemisorption,giving rise to molecule/colloid formation of oleate and Fe―OL complex compound.Time-of-flight secondary ion mass spectrometry(ToF-SIMS)results demonstrated that oleate species adsorbed onto the hematite surfaces with a thickness of a few nanometers.Furthermore,the normalized peak intensity of C4H7+ions on the hematite sample at pH 8.2 increased remarkably comparing with corresponding result of hematite sample at pH 6.8.The new findings of the present study well revealed the dissolution of microfine hematite and the pH effects on the hematite flotation,as well as the adsorption characteristics of oleate species.展开更多
Previous research has documented that solid biomaterials such as charcoal or waste coffee and tea have been used to remove heavy metals from contaminated aqueous solutions through adsorption. However, these studies us...Previous research has documented that solid biomaterials such as charcoal or waste coffee and tea have been used to remove heavy metals from contaminated aqueous solutions through adsorption. However, these studies used very low heavy metal concentrations between 10 to 100 ppm. Recently published research work reported that extracts of edible plants and fruits were able to effectively remove lead from contaminated aqueous solution. This paper evaluates the ability of charcoal, un-brewed coffee and tea, fishbone, and caffeine to remove lead from contaminated aqueous solutions. The order of lead removal from 1300 ppm of lead solution is Charcoal (100%) > Tea (97%) > Coffee Ground (88%) > Instant Coffee (83.5%) > Coffee Bean (82%) > Fishbone (76%) > Caffeine (1.3%). These results clearly demonstrate that not all solid biomaterials can adsorb lead and that caffeine, a component of coffee and tea does not participate in the removal of lead from contaminated solutions. Furthermore, the results suggest that two possible processes may be involved in the reactions presented here: adsorption of lead by the solid substrates and precipitation of lead by the solubilized biochemical components of the substrates.展开更多
The flocculation effects of homemade hydroxamated flocculant(HPAA)and commercially available sodium polyacrylate(PAAS)on synthetic goethite suspensions with different solid contents were studied.The adsorption mechani...The flocculation effects of homemade hydroxamated flocculant(HPAA)and commercially available sodium polyacrylate(PAAS)on synthetic goethite suspensions with different solid contents were studied.The adsorption mechanism of HPAA or PAAS on the surfaces of goethite was investigated.The settling rate of 50 g/L goethite suspension with HPAA(1.74 m/h)was faster than that with PAAS(0.54 m/h),which indicated that HPAA exhibits better flocculation performance than PAAS does.It could be found that the stretching vibration of carbonyl band in hydroxamic acid groups of HPAA was downshifted from 1 654 cm^(-1) to 1 645 cm^(-1) and a new adsorption band appeared at 1 455 cm-1,which demonstrated that a five-membered ring chelate may be formed among iron atoms of goethite surfaces,the hydroxyl groups and the carbonyl groups in hydroxamic acid groups of HPAA.In the case of PAAS,the separation of the asymmetric and symmetric stretches of the carboxylate groups in adsorbed PAAS was 163 cm-1,which was greater than that of unadsorbed PAAS with 157 cm^(-1).There was no indication of a contribution from the monodentate adsorption between iron atoms of goethite surfaces and carboxylate groups of PAAS,but there may exist a bi-dentate bridging structure.Compared with synthetic goethite,XPS curve fittings of Fe 2p spectra showed that the binding energies of the main Fe 2p3/2 and Fe 2p1/2 resolved peaks on HPAA-treated goethite surfaces were correspondingly decreased by 0.9 and 0.7 e V,while those on PAAS-treated goethite surfaces were correspondingly decreased by 0.7 and 0.3 e V.The characteristic N 1s peak of HPAA and C 1s peak of PAAS were correspondingly detected on HPAA-treated and PAAS-treated goethites,and a binding energy change of N 1s spectrum of adsorbed HPAA was observed.The relative atomic ratios of C/Fe,N/Fe and O/Fe on HPAA-treated and PAAS-treated goethite surfaces were increased.All the results suggested that HPAA or PAAS was adsorbed on the goethite surfaces by the chemisorption,and a stronger adsorption of HPAA on the goethite surfaces happened than that of PAAS.展开更多
Removal of Cr（VI） from aqueous solution by strong alkaline anion exchange fiber （SAAEF） was achieved using batch adsorption experiments. The effect of contact time, initial Cr（VI） concentration and pH was invest...Removal of Cr（VI） from aqueous solution by strong alkaline anion exchange fiber （SAAEF） was achieved using batch adsorption experiments. The effect of contact time, initial Cr（VI） concentration and pH was investigated. The results showed that the maximum adsorption capacity of SAAEF was 187.7 mg/g at pH=1.0. The adsorption capacity increased with Cr（VI） concentration but decreased with pH value when pH〉1.0. Adsorption isotherms at various temperatures were obtained. Langmuir, Freundlich, Dubinin-Radushkevich and Temkin models were adopted and the equilibrium data fitted best with the Langmuir isotherm. The constants of these models indicated that the adsorption process involved both chemisorption and physisorption. The values of thermodynamic parameters, including DH, DG and DS, suggested that the adsorption of Cr（VI） on SAAEF was a spontaneous, entropy-driven and endothermic process. Q（iso） was not a constant value, which indicated an inhomogenous energy distribution on SAAEF.展开更多
The influence of pulp temperature on the floatability and adsorption behavior of fine wolframite with sodium oleate was investigated by microflotation experiments, electric conductivity tests, adsorption measurements,...The influence of pulp temperature on the floatability and adsorption behavior of fine wolframite with sodium oleate was investigated by microflotation experiments, electric conductivity tests, adsorption measurements, and FT-IR analysis. Microflotation results show that fine wolframite with sodium oleate exhibits a good floatability at pH 8–9. Electric conductivity tests indicate that the high temperature enhances the ionization degree and electric mobility of oleate species, then the flotation recovery of fine wolframite and the adsorption amount of sodium oleate are observed to increase with the rise in pulp temperature. The results of adsorption experiments are found to meet Freundlich isotherms successfully, and the isosteric enthalpy （ΔH^Θ） is in conformity with the chemical bonding. The changes in FT-IR analysis provide sufficient evidence that sodium oleate interacts with the metal cations of wolframite surface, and the increase in pulp temperature clearly promotes the chemisorption intensity. These findings will be beneficial to strengthen the flotation behavior of fine wolframite.展开更多
For the first time, a series of alkynyl carbon materials（ACMs） were prepared via the mechanochemical reaction of CaC2 with six polyhalogenated precursors, namely CCl4,C2Cl6, C2Cl4, C6Cl6, C6Br6, and C14H4Br10（ACM-1...For the first time, a series of alkynyl carbon materials（ACMs） were prepared via the mechanochemical reaction of CaC2 with six polyhalogenated precursors, namely CCl4,C2Cl6, C2Cl4, C6Cl6, C6Br6, and C14H4Br10（ACM-1, ACM-2, ACM-3, ACM-4, ACM-5, and ACM-6,respectively） and used for the adsorptive removal of mercury from aqueous solutions.Based on preliminary investigations, the adsorption of mercury on ACM-5 was studied in depth. Specifically, the effect of p H on mercury adsorptivity, adsorption kinetics,thermodynamics, isotherms, and recyclability was studied. The adsorptivity of mercury on ACMs was found to be closely related to the hydrocarbon precursor, specific surface area of sorbent, and the alkynyl content. ACM-5 showed the best performance and is among the best raw carbonaceous sorbents reported so far, with a Langmuir saturated adsorption capacity of 191.9 mg g-1. The promising mercury adsorption performance mainly arises from the strong Lewis soft acid–soft base interactions between the alkynyl groups and mercury ions. The adsorption isotherms could be satisfactorily correlated with the Langmuir equation. The results show that the ACMs can be used as efficient sorbents for the removal of mercury and may also be useful for the adsorption of other heavy metals.展开更多
A hypercrosslinked adsorption resin （ZH-05） modified by N-acetylaniline in the post crosslinking process was prepared. The adsorption properties of ZH-05 toward 2,4-dichlorophenol in comparison with granular activat...A hypercrosslinked adsorption resin （ZH-05） modified by N-acetylaniline in the post crosslinking process was prepared. The adsorption properties of ZH-05 toward 2,4-dichlorophenol in comparison with granular activated carbon （GAC） and Amberlite XAD-4 were observed. The present study mainly focuses on the static equilibrium adsorption behaviors, desorption profiles and the proof of chemisorption. The results show that the Langmuir equation can give a perfect fitting to experimental data, and high temperature was favorable for adsorption of 2,4-dichlorophenol on ZH-05. A related equation was used to correlate the amount of chemisorption and the suppositionai chemisorption equilibrium concentration of adsorbate in aqueous solution. The adsorption capacities from different ranges of temperature and the static desorption experiment both reveal the same conclusion, i.e., the adsorption of 2,4-dichlorophenol from water on ZH-05 is a coexistent process of physical adsorption and chemical transition as on GAC.展开更多
A series of novel carbon nanofibers(CNFs)based Cu-ZrO2 catalysts were synthesized by deposition precipitation method.To investigate the influence of promoter,catalysts were loaded with 1,2,3 and 4 wt%ZnO and character...A series of novel carbon nanofibers(CNFs)based Cu-ZrO2 catalysts were synthesized by deposition precipitation method.To investigate the influence of promoter,catalysts were loaded with 1,2,3 and 4 wt%ZnO and characterized by ICP-OES,HRTEM,BET,N2O chemisorption,TPR,XPS and CO2-TPD techniques.The results revealed that physicochemical properties of the catalysts were strongly influenced by incorporation of ZnO to the parent catalyst.Copper surface area(SCu)and dispersion(DCu)were slightly decreased by incorporation of ZnO promoter.Nevertheless,SCuand DCuwere remarkably decreased when ZnO content was exceeded beyond 3 wt%.The catalytic performance was evaluated by using autoclave slurry reactor at a pressure and temperature of 30 bar and 180℃,respectively.The promotion of CuZrO2/CNFs catalyst with 3 wt%of ZnO enhanced methanol synthesis rate from 32 to 45 g kg^-1 h^-1.Notably,with the ZnO promotion the selectivity to methanol was enhanced to 92%compared to 78%of the un-promoted Cu-ZrO2/CNFs catalyst at the expense of a lowered CO2 conversion.In addition,the catalytic activity of this novel catalyst system for CO2 hydrogenation to methanol was compared with the recent literature data.展开更多
Carbon nanofibers films are typical flexible electrode in the field of energy storage,but their application in Zinc-ion hybrid capacitors(ZIHCs)is limited by the low energy density due to the lack of active adsorption...Carbon nanofibers films are typical flexible electrode in the field of energy storage,but their application in Zinc-ion hybrid capacitors(ZIHCs)is limited by the low energy density due to the lack of active adsorption sites.In this work,an in-situ exfoliation strategy is reported to modulate the chemisorption sites of carbon nanofibers by high pyridine/pyrrole nitrogen doping and carbonyl functionalization.The experimental results and theoretical calculations indicate that the highly electronegative pyridine/pyrrole nitrogen dopants can not only greatly reduce the binding energy between carbonyl group and Z n2+by inducing charge delocalization of the carbonyl group,but also promote the adsorption of Zn2+by bonding with the carbonyl group to form N–Zn–O bond.Benefit from the multiple highly active chemisorption sites generated by the synergy between carbonyl groups and pyridine/pyrrole nitrogen atoms,the resulting carbon nanofibers film cathode displays a high energy density,an ultralong-term lifespan,and excellent capacity reservation under commercial mass loading(14.45 mg cm-2).Particularly,the cathodes can also operate stably in flexible or quasi-solid devices,indicating its application potential in flexible electronic products.This work established a universal method to solve the bottleneck problem of insufficient active adsorption sites of carbon-based ZIHCs.Imoproved should be changed into Improved.展开更多
In contrast to the exploration of novel photocatalytic materials,vacancy engineering of traditionalphotocatalysts comprising earth‐abundant elements represents an effective method for enhancingphotocatalytic performa...In contrast to the exploration of novel photocatalytic materials,vacancy engineering of traditionalphotocatalysts comprising earth‐abundant elements represents an effective method for enhancingphotocatalytic performance without introducing alien elements.This minireview analyzes the latestprogress in engineering vacancies in photocatalysts,remarks on state‐of‐the‐art characterizationtechniques for vacancies,and reviews the formation chemistry and fundamental benefits of anionand cation vacancies in typical photocatalysts.Although knowledge of these vacancies is increasing,challenges remain in this field,and possible further research is therefore also discussed.展开更多
Steelmaking industry faces urgent demands for both steel slag utilization and CO_(2)abatement.Ca and Mg of steel slag can be extracted by acid solution and used to prepare sorbents for CO_(2)capture.In this work,the c...Steelmaking industry faces urgent demands for both steel slag utilization and CO_(2)abatement.Ca and Mg of steel slag can be extracted by acid solution and used to prepare sorbents for CO_(2)capture.In this work,the calcium-based sorbents were prepared from stainless steel slag leachate by co-precipitation,and the initial CO_(2)chemisorption capacity of the calcium-based sorbent prepared from steel slag with the Ca and Mg molar ratio of 3.64:1 was 0.40 g/g.Moreover,the effect of Ca/Mg molar ratio on the morphology,structure,and CO_(2)chemisorption capacity of the calcium-based sorbents were investigated.The results show that the optimal Ca/Mg molar ratio of sorbent for CO_(2)capture was4.2:1,and the skeleton support effect of MgO in calcium-based sorbents was determined.Meanwhile,the chemisorption kinetics of the sorbents was studied using the Avrami-Erofeev model.There were two processes of CO_(2)chemisorption,and the activation energy of the first stage(reaction control)was found to be lower than that of the second stage(diffusion control).展开更多
The effects of promoters K, Ba, Sm on the chemisorption and desorption of hydrogen and nitrogen, dispersion of metallic Ru. and catalytic activity of active carbon (AC) supported ruthenium catalyst for ammonia synthes...The effects of promoters K, Ba, Sm on the chemisorption and desorption of hydrogen and nitrogen, dispersion of metallic Ru. and catalytic activity of active carbon (AC) supported ruthenium catalyst for ammonia synthesis have been studied by means of pulse chromatography, temperature-programmed desorption, and activity test. Promoters K, Ba and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly, and particularly, potassium exhibited the best promotion on the activity because of the strong electronic donation to metallic Ru. Much higher activity can be obtained for Ru/AC catalyst with binary or triple promoters. The activity of Ru/AC catalyst is dependent on the adsorption of hydrogen and nitrogen. The high activity of catalyst could be ascribed to strong dissociation of nitrogen on the catalyst surface. Strong adsorption of hydrogen would inhibit the adsorption of nitrogen, resulted in decrease of the catalytic activity. Ru/AC catalyst promoted by Sm2O3 shows the best dispersion of metallic Ru, since the partly reduced SmOx on the surface modifies the morphology of active sites and favors the dispersion of metallic Ru. The activity of Ru/AC catalysts is in accordance to the corresponding amount of nitrogen chemisorption and the desorption activation energy of nitrogen. The desorption activation energy for nitrogen decreases in the order of Ru>Ru-Ba>Ru-Sm>Ru-Ba-Sm>Ru-K>Ru-K-Sm>Ru-K-Ba>Ru-K-Ba-Sm, just opposite to the order of catalytic activity, suggesting that the ammonia synthesis over Ru-based catalyst is controlled by the step of dissociation of nitrogen.展开更多
基金financial support from the National Natural Science Foundation of China(Nos.22278011,22225803,22038001 and 22108007)Beijing Natural Science Foundation(No.Z230023)+1 种基金The Science&Technology Project of Beijing Municipal Education Committee(No.KZ201810005004)Beijing Nova Program(No.Z211100002121094)。
文摘Large-scale deployment of carbon dioxide(CO_(2))removal technology is an essential step to cope with global warming and achieve carbon neutrality.Direct air capture(DAC)has recently received increasing attention given the high flexibility to remove CO_(2)from discrete sources.Porous materials with adjustable pore characteristics are promising sorbents with low or no latent heat of vaporization.This review article has summarized the recent development of porous sorbents for DAC,with a focus of pore engineering strategy and adsorption mechanism.Physisorbents such as zeolites,porous carbons,metal-organic frameworks(MOFs),and amine-modified chemisorbents have been discussed and their challenges in practical application have been analyzed.At last,future directions have been proposed,and it is expected to inspire collaborations from chemistry,environment,material science and engineering communities.
基金supported by Shanghai Pujiang Program(No.21PJ1400400)the Research Start-up Fund at Donghua University+2 种基金the Foundation of State Key Laboratory of Coal Combustion(No.FSKLCCA2309)the National Natural Science Foundation of China(No.22302109)the Australian Research Council(No.DP230102740)。
文摘In this work,we developed plasmonic photocatalyst composed of Cu Pd alloy nanoparticles supported on Ti N,the optimized Cu_(3)Pd_(2)/Ti N catalyst shows excellent conversion(>96%)and selectivity(>99%)for Heck reaction at 50℃ under visible light irradiation.By in-situ spectroscopic investigations,we find that visible light excitation could achieve stable metallic Cu species on the surface of Cu Pd alloy nanoparticles,thereby eliminating the inevitable surface oxides of Cu based catalyst.The in-situ formed metallic Cu species under irradiation take advantage of the strong interactions of Cu with visible light,and manifest in the localized surface plasmon resonances(LSPR)photoexcitation.Visible light excitation could further promote the charge transfer between catalytic Pd component and the support Ti N,resulting in electron-rich Pd sites on Cu Pd/Ti N.Moreover,light excitation on Cu Pd/Ti N generates strong chemisorption of iodobenzene and styrene,favoring the activation of reactants for Heck reaction.DFT calculations suggest that electron-rich Cu Pd sites ideally lower the activation energy barrier for the coupling reaction.This work provides valuable insights for mechanistic understanding of plasmonic photocatalysis.
基金supported by the National Key R&D Program of China(No.2018YFE0203003)the National Natural Science Foundation of China(Nos.22173101,22173099,22288201,21703242)+3 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0970203)the Innovation Program for Quantum Science and Technology(No.2021ZD0303305)Dalian Talents Innovation Support Program(No.2021RD05)the Open Fund(SKLMRD-K202508)of the State Key Laboratory of Molecular Reaction Dynamics in Dalian Institute of Chemical Physics,Chinese Academy of Sciences.The computational resources are supported by SongShan Lake HPC Center(SSL-HPC)in Great Bay University.
文摘In this study,six-dimensional(6D)time-dependent wave packet calcula-tions were employed to investigate the dissociation of HCl molecules on two bimetallic surfaces,Cu/Ag(111)and Cu/Au(111).These calculations were based on two accurate potential energy surfaces(PESs)constructed using neu-ral network methodology.Density functional theory(DFT)calculations revealed that the static barrier heights for HCl on Cu/Ag(111)and Cu/Au(111)were 0.32 eV and 0.28 eV,respectively.These values are significantly lower than the barrier height on pure Cu(111)(0.52 eV),primarily due to surface strain effects.However,it was found that the 6D dissociation probability of HCl in(v=0,1,j=0)states on Cu/Au(111)was considerably lower,despite its barrier height being 0.04 eV lower than that for Cu/Ag(111).The underlying mechanism for this observation was attributed to the non-monotonic dependence of the minimum energy path(MEP)on the molecular orientation,which was induced by charge transfer effect for HCl+Cu/Au(111).In contrast,HCl+Cu/Ag(111)exhibited a monotonic dependence.These contrasting behaviors led to dis-tinct differences in rotational alignment and excitation effects for the two reactions.
基金financially supported by the Natural Science Foundation of Shandong(ZR2023ME014)。
文摘Electrocatalysis has been extensively explored for the storage and conversion of renewable electric power.Understanding the physisorption and chemisorption processes at electrified solid–liquid interfaces(ESLIs)is crucial for revealing the typical surface restructuring and catalyst dissolution during electrocatalysis.Although advanced in situ tools and theoretical models have been proposed[1,2],identifying the nature of the active sites with atomic-scale spatial resolution remains a challenge,especially at ESLIs.In a recent work published in Nature,Zhang et al.[3]reported a groundbreaking atomic-resolution imaging of the structural dynamics of Cu nanowire catalysts in ESLIs for electrochemical CO_(2)reduction(ECR).
文摘Carbon capture and storage(CCS)is an advanced environmental technology for mitigating CO_(2) emissions and addressing climate change.Among the various approaches,adsorption has emerged as a promising method for CO_(2) capture due to its effiectiveness and practicality.This review explores the potential of clay minerals as adsorbents for CO_(2) capture,providing an in-depth analysis of their inherent properties and the mechanisms involved in adsorption process.The review begins with an introduction to CCS and the concept of adsorption,followed by a detailed examination of various clay minerals,including sepiolite,montmorillonite,bentonite,kaolinite,saponite,halloysite,and illite.Each mineral’s suitability for CO_(2) adsorption is assessed,highlighting the specific properties that contribute to their performance.The mechanisms of CO_(2) adsorption including physisorption,chemisorption,ion exchange,pore diffusion,intraparticle diffusion,surface complexation,and competitive adsorption are thoroughly discussed.The review also covers the modification of clay minerals through physical and chemical treatments,amine functionalization,and composite formation to enhance their CO_(2) adsorption capacity.Additionally,regeneration methods such as temperature-swing adsorption(TSA),pressure-swing adsorption(PSA),and purging are discussed,along with CO_(2) recovery and storage techniques for improving energy efficiency.The review concludes with an overview of characterization methods for clay-based adsorbents and potential applications,while addressing the challenges and future trends in thefield.This work emphasizes the promising role of clay-based adsorbents in advancing CCS technology.
基金This work was carried out in the framework of PAPIIT-UNAM(IN-205823)project.
文摘Li_(6)ZnO_(4)was chemically modified by nickel addition,in order to develop different compositions of the solid solution Li_(6)Zn_(1-x)Ni_(x)O_(4).These materials were evaluated bifunctionally;analyzing their CO_(2)capture performances,aswell as on their catalytic properties for H_(2)production via dry reforming of methane(DRM).The crystal structures of Li_(6)Zn_(1-x)Ni_(x)O_(4)solid solution samples were determined through X-ray diffraction,which confirmed the integration of nickel ions up to a concentration around 20 mol%,meanwhile beyond this value,a secondary phase was detected.These results were supported by XPS and TEM analyses.Then,dynamic and isothermal thermogravimetric analyses of CO_(2)capture revealed that Li_(6)Zn_(1-x)Ni_(x)O_(4)solid solution samples exhibited good CO_(2)chemisorption efficiencies,similarly to the pristine Li_(6)ZnO_(4)chemisorption trends observed.Moreover,a kinetic analysis of CO_(2)isothermal chemisorptions,using the Avrami-Erofeev model,evidenced an increment of the constant rates as a function of the Ni content.Since Ni^(2+)ions incorporation did not reduce the CO_(2)capture efficiency and kinetics,the catalytic properties of thesematerialswere evaluated in the DRM process.Results demonstrated that nickel ions favored hydrogen(H_(2))production over the pristine Li_(6)ZnO_(4)phase,despite a second H2 production reaction was determined,methane decomposition.Thereby,Li_(6)Zn_(1-x)Ni_(x)O_(4)ceramics can be employed as bifunctional materials.
基金supported by the National Natural Science Foundation of China(22109020 and 22109082).
文摘Heterogeneous catalysis remains at the core of various bulk chemical manufacturing and energy conversion processes,and its revolution necessitates the hunt for new materials with ideal catalytic activities and economic feasibility.Computational high-throughput screening presents a viable solution to this challenge,as machine learning(ML)has demonstrated its great potential in accelerating such processes by providing satisfactory estimations of surface reactivity with relatively low-cost information.This review focuses on recent progress in applying ML in adsorption energy prediction,which predominantly quantifies the catalytic potential of a solid catalyst.ML models that leverage inputs from different categories and exhibit various levels of complexity are classified and discussed.At the end of the review,an outlook on the current challenges and future opportunities of ML-assisted catalyst screening is supplied.We believe that this review summarizes major achievements in accelerating catalyst discovery through ML and can inspire researchers to further devise novel strategies to accelerate materials design and,ultimately,reshape the chemical industry and energy landscape.
基金financially supported by the Certificate of postdoctoral research grant in Henan province,the Natural Science Foundation of Henan province(Grant No.212300410281)the National Natural Science Foundation of China(Grant No.21975225).
文摘Lithium-sulfur batteries(LSBs)with high energy densities have been demonstrated the potential for energy-intensive demand applications.However,their commercial applicability is hampered by hysteretic electrode reaction kinetics and the shuttle effect of lithium polysulfides(LiPSs).In this work,an interlayer consisting of high-entropy metal oxide(Cu_(0.7)Fe_(0.6)Mn_(0.4)Ni_(0.6)Sn_(0.5))O_(4) grown on carbon nanofibers(HEO/CNFs)is designed for LSBs.The CNFs with highly porous networks provide transport pathways for Li^(+) and e^(-),as well as a physical sieve effect to limit LiPSs crossover.In particular,the grapevine-like HEO nanoparticles generate metal-sulfur bonds with LiPSs,efficiently anchoring active materials.The unique structure and function of the interlayer enable the LSBs with superior electrochemical performance,i.e.,the high specific capacity of 1381 mAh g^(-1) at 0.1 C and 561 mAh g^(-1) at 6 C.This work presents a facile strategy for exploiting high-performance LSBs.
基金supported by the Natural Science Foundation of China (No. 52164021)the Natural Science Foundation of Yunnan Province (No. 2019FB078)
文摘The adsorption of sodium oleate(NaOL)at the microfine hematite/aqueous solution interface was investigated in this paper.Experimental research indicated that negative effects stemmed from the dissolution of the microfine hematite(D50=19.21μm)could be effectively eliminated via the appropriate dosage of NaOL at alkali pH conditions.Solution chemistry calculation and adsorption test results indicated that RCOOand(RCOO)_(2)^(2-) ions were responsible for microfine hematite flotation at pH 8.2.Zeta potential and FTIR measurements confirmed the co-adsorption of molecular and ionic oleate species occurred at pH 8.2.X-ray photoelectron spectroscopy(XPS)results further indicated that oleate species interacted with hematite surfaces mainly through chemisorption,giving rise to molecule/colloid formation of oleate and Fe―OL complex compound.Time-of-flight secondary ion mass spectrometry(ToF-SIMS)results demonstrated that oleate species adsorbed onto the hematite surfaces with a thickness of a few nanometers.Furthermore,the normalized peak intensity of C4H7+ions on the hematite sample at pH 8.2 increased remarkably comparing with corresponding result of hematite sample at pH 6.8.The new findings of the present study well revealed the dissolution of microfine hematite and the pH effects on the hematite flotation,as well as the adsorption characteristics of oleate species.
文摘Previous research has documented that solid biomaterials such as charcoal or waste coffee and tea have been used to remove heavy metals from contaminated aqueous solutions through adsorption. However, these studies used very low heavy metal concentrations between 10 to 100 ppm. Recently published research work reported that extracts of edible plants and fruits were able to effectively remove lead from contaminated aqueous solution. This paper evaluates the ability of charcoal, un-brewed coffee and tea, fishbone, and caffeine to remove lead from contaminated aqueous solutions. The order of lead removal from 1300 ppm of lead solution is Charcoal (100%) > Tea (97%) > Coffee Ground (88%) > Instant Coffee (83.5%) > Coffee Bean (82%) > Fishbone (76%) > Caffeine (1.3%). These results clearly demonstrate that not all solid biomaterials can adsorb lead and that caffeine, a component of coffee and tea does not participate in the removal of lead from contaminated solutions. Furthermore, the results suggest that two possible processes may be involved in the reactions presented here: adsorption of lead by the solid substrates and precipitation of lead by the solubilized biochemical components of the substrates.
基金Supported by the National Natural Science Foundation of China(No.5117423151134007)
文摘The flocculation effects of homemade hydroxamated flocculant(HPAA)and commercially available sodium polyacrylate(PAAS)on synthetic goethite suspensions with different solid contents were studied.The adsorption mechanism of HPAA or PAAS on the surfaces of goethite was investigated.The settling rate of 50 g/L goethite suspension with HPAA(1.74 m/h)was faster than that with PAAS(0.54 m/h),which indicated that HPAA exhibits better flocculation performance than PAAS does.It could be found that the stretching vibration of carbonyl band in hydroxamic acid groups of HPAA was downshifted from 1 654 cm^(-1) to 1 645 cm^(-1) and a new adsorption band appeared at 1 455 cm-1,which demonstrated that a five-membered ring chelate may be formed among iron atoms of goethite surfaces,the hydroxyl groups and the carbonyl groups in hydroxamic acid groups of HPAA.In the case of PAAS,the separation of the asymmetric and symmetric stretches of the carboxylate groups in adsorbed PAAS was 163 cm-1,which was greater than that of unadsorbed PAAS with 157 cm^(-1).There was no indication of a contribution from the monodentate adsorption between iron atoms of goethite surfaces and carboxylate groups of PAAS,but there may exist a bi-dentate bridging structure.Compared with synthetic goethite,XPS curve fittings of Fe 2p spectra showed that the binding energies of the main Fe 2p3/2 and Fe 2p1/2 resolved peaks on HPAA-treated goethite surfaces were correspondingly decreased by 0.9 and 0.7 e V,while those on PAAS-treated goethite surfaces were correspondingly decreased by 0.7 and 0.3 e V.The characteristic N 1s peak of HPAA and C 1s peak of PAAS were correspondingly detected on HPAA-treated and PAAS-treated goethites,and a binding energy change of N 1s spectrum of adsorbed HPAA was observed.The relative atomic ratios of C/Fe,N/Fe and O/Fe on HPAA-treated and PAAS-treated goethite surfaces were increased.All the results suggested that HPAA or PAAS was adsorbed on the goethite surfaces by the chemisorption,and a stronger adsorption of HPAA on the goethite surfaces happened than that of PAAS.
基金Project (20080242009) supported by Basic Research Foundation of Beijing Institute of Technology, China
文摘Removal of Cr（VI） from aqueous solution by strong alkaline anion exchange fiber （SAAEF） was achieved using batch adsorption experiments. The effect of contact time, initial Cr（VI） concentration and pH was investigated. The results showed that the maximum adsorption capacity of SAAEF was 187.7 mg/g at pH=1.0. The adsorption capacity increased with Cr（VI） concentration but decreased with pH value when pH〉1.0. Adsorption isotherms at various temperatures were obtained. Langmuir, Freundlich, Dubinin-Radushkevich and Temkin models were adopted and the equilibrium data fitted best with the Langmuir isotherm. The constants of these models indicated that the adsorption process involved both chemisorption and physisorption. The values of thermodynamic parameters, including DH, DG and DS, suggested that the adsorption of Cr（VI） on SAAEF was a spontaneous, entropy-driven and endothermic process. Q（iso） was not a constant value, which indicated an inhomogenous energy distribution on SAAEF.
基金Project(51704058)supported by the National Natural Science Foundation of China
文摘The influence of pulp temperature on the floatability and adsorption behavior of fine wolframite with sodium oleate was investigated by microflotation experiments, electric conductivity tests, adsorption measurements, and FT-IR analysis. Microflotation results show that fine wolframite with sodium oleate exhibits a good floatability at pH 8–9. Electric conductivity tests indicate that the high temperature enhances the ionization degree and electric mobility of oleate species, then the flotation recovery of fine wolframite and the adsorption amount of sodium oleate are observed to increase with the rise in pulp temperature. The results of adsorption experiments are found to meet Freundlich isotherms successfully, and the isosteric enthalpy （ΔH^Θ） is in conformity with the chemical bonding. The changes in FT-IR analysis provide sufficient evidence that sodium oleate interacts with the metal cations of wolframite surface, and the increase in pulp temperature clearly promotes the chemisorption intensity. These findings will be beneficial to strengthen the flotation behavior of fine wolframite.
文摘For the first time, a series of alkynyl carbon materials（ACMs） were prepared via the mechanochemical reaction of CaC2 with six polyhalogenated precursors, namely CCl4,C2Cl6, C2Cl4, C6Cl6, C6Br6, and C14H4Br10（ACM-1, ACM-2, ACM-3, ACM-4, ACM-5, and ACM-6,respectively） and used for the adsorptive removal of mercury from aqueous solutions.Based on preliminary investigations, the adsorption of mercury on ACM-5 was studied in depth. Specifically, the effect of p H on mercury adsorptivity, adsorption kinetics,thermodynamics, isotherms, and recyclability was studied. The adsorptivity of mercury on ACMs was found to be closely related to the hydrocarbon precursor, specific surface area of sorbent, and the alkynyl content. ACM-5 showed the best performance and is among the best raw carbonaceous sorbents reported so far, with a Langmuir saturated adsorption capacity of 191.9 mg g-1. The promising mercury adsorption performance mainly arises from the strong Lewis soft acid–soft base interactions between the alkynyl groups and mercury ions. The adsorption isotherms could be satisfactorily correlated with the Langmuir equation. The results show that the ACMs can be used as efficient sorbents for the removal of mercury and may also be useful for the adsorption of other heavy metals.
基金This work was supported by the Educational Bureau (No.05KJD610250)the Science & Technology Bureau (No. BS2006032) of Jiangsu Province, China.
文摘A hypercrosslinked adsorption resin （ZH-05） modified by N-acetylaniline in the post crosslinking process was prepared. The adsorption properties of ZH-05 toward 2,4-dichlorophenol in comparison with granular activated carbon （GAC） and Amberlite XAD-4 were observed. The present study mainly focuses on the static equilibrium adsorption behaviors, desorption profiles and the proof of chemisorption. The results show that the Langmuir equation can give a perfect fitting to experimental data, and high temperature was favorable for adsorption of 2,4-dichlorophenol on ZH-05. A related equation was used to correlate the amount of chemisorption and the suppositionai chemisorption equilibrium concentration of adsorbate in aqueous solution. The adsorption capacities from different ranges of temperature and the static desorption experiment both reveal the same conclusion, i.e., the adsorption of 2,4-dichlorophenol from water on ZH-05 is a coexistent process of physical adsorption and chemical transition as on GAC.
基金the Ministry of Higher Education Malaysia for providing financial support to this work via FRGS No:FRGS/1/2011/SG/UTP/02/13Universiti Teknologi PETRONAS
文摘A series of novel carbon nanofibers(CNFs)based Cu-ZrO2 catalysts were synthesized by deposition precipitation method.To investigate the influence of promoter,catalysts were loaded with 1,2,3 and 4 wt%ZnO and characterized by ICP-OES,HRTEM,BET,N2O chemisorption,TPR,XPS and CO2-TPD techniques.The results revealed that physicochemical properties of the catalysts were strongly influenced by incorporation of ZnO to the parent catalyst.Copper surface area(SCu)and dispersion(DCu)were slightly decreased by incorporation of ZnO promoter.Nevertheless,SCuand DCuwere remarkably decreased when ZnO content was exceeded beyond 3 wt%.The catalytic performance was evaluated by using autoclave slurry reactor at a pressure and temperature of 30 bar and 180℃,respectively.The promotion of CuZrO2/CNFs catalyst with 3 wt%of ZnO enhanced methanol synthesis rate from 32 to 45 g kg^-1 h^-1.Notably,with the ZnO promotion the selectivity to methanol was enhanced to 92%compared to 78%of the un-promoted Cu-ZrO2/CNFs catalyst at the expense of a lowered CO2 conversion.In addition,the catalytic activity of this novel catalyst system for CO2 hydrogenation to methanol was compared with the recent literature data.
基金funds from the National Natural Science Foundation of China(51772082,51804106,and 51574117)the Natural Science Foundation of Hunan Province(2019JJ30002,2019JJ50061 and 2020CB1007)Natural Science Foundation of Guangdong Providence(2018A030310571)。
文摘Carbon nanofibers films are typical flexible electrode in the field of energy storage,but their application in Zinc-ion hybrid capacitors(ZIHCs)is limited by the low energy density due to the lack of active adsorption sites.In this work,an in-situ exfoliation strategy is reported to modulate the chemisorption sites of carbon nanofibers by high pyridine/pyrrole nitrogen doping and carbonyl functionalization.The experimental results and theoretical calculations indicate that the highly electronegative pyridine/pyrrole nitrogen dopants can not only greatly reduce the binding energy between carbonyl group and Z n2+by inducing charge delocalization of the carbonyl group,but also promote the adsorption of Zn2+by bonding with the carbonyl group to form N–Zn–O bond.Benefit from the multiple highly active chemisorption sites generated by the synergy between carbonyl groups and pyridine/pyrrole nitrogen atoms,the resulting carbon nanofibers film cathode displays a high energy density,an ultralong-term lifespan,and excellent capacity reservation under commercial mass loading(14.45 mg cm-2).Particularly,the cathodes can also operate stably in flexible or quasi-solid devices,indicating its application potential in flexible electronic products.This work established a universal method to solve the bottleneck problem of insufficient active adsorption sites of carbon-based ZIHCs.Imoproved should be changed into Improved.
基金supported by the National Natural Science Foundation of China (21377084)Special Fund for Agro-scientific Research in the Public Interest (201503107)~~
文摘In contrast to the exploration of novel photocatalytic materials,vacancy engineering of traditionalphotocatalysts comprising earth‐abundant elements represents an effective method for enhancingphotocatalytic performance without introducing alien elements.This minireview analyzes the latestprogress in engineering vacancies in photocatalysts,remarks on state‐of‐the‐art characterizationtechniques for vacancies,and reviews the formation chemistry and fundamental benefits of anionand cation vacancies in typical photocatalysts.Although knowledge of these vacancies is increasing,challenges remain in this field,and possible further research is therefore also discussed.
基金financially supported by the National Natural Science Foundation of China(No.52074078)the National Key R&D Program of China(No.2021YFC2901200)+4 种基金the Applied Fundamental Research Program of Liaoning Province(No.2023JH2/101600002)the Liaoning Provincial Natural Science Foundation of China(No.2022-YQ-09)the Shenyang Young Middle-Aged Scientific and Technological Innovation Talent Support Program,China(No.RC220491)the Liaoning Province Steel Industry-University-Research Innovation Alliance Cooperation Project of Bensteel Group,China(No.KJBLM202202)the Fundamental Research Funds for the Central Universities,China(Nos.N2201023,N2325009)。
文摘Steelmaking industry faces urgent demands for both steel slag utilization and CO_(2)abatement.Ca and Mg of steel slag can be extracted by acid solution and used to prepare sorbents for CO_(2)capture.In this work,the calcium-based sorbents were prepared from stainless steel slag leachate by co-precipitation,and the initial CO_(2)chemisorption capacity of the calcium-based sorbent prepared from steel slag with the Ca and Mg molar ratio of 3.64:1 was 0.40 g/g.Moreover,the effect of Ca/Mg molar ratio on the morphology,structure,and CO_(2)chemisorption capacity of the calcium-based sorbents were investigated.The results show that the optimal Ca/Mg molar ratio of sorbent for CO_(2)capture was4.2:1,and the skeleton support effect of MgO in calcium-based sorbents was determined.Meanwhile,the chemisorption kinetics of the sorbents was studied using the Avrami-Erofeev model.There were two processes of CO_(2)chemisorption,and the activation energy of the first stage(reaction control)was found to be lower than that of the second stage(diffusion control).
基金Supported by the Natural Science Foundation of Zhejiang Province (No. 299015), the Development Plan of Youth Mainstay Teacher of the Education Ministry of China and the Special Foundation for Youth Talent by Zhejiang (RC9702).
文摘The effects of promoters K, Ba, Sm on the chemisorption and desorption of hydrogen and nitrogen, dispersion of metallic Ru. and catalytic activity of active carbon (AC) supported ruthenium catalyst for ammonia synthesis have been studied by means of pulse chromatography, temperature-programmed desorption, and activity test. Promoters K, Ba and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly, and particularly, potassium exhibited the best promotion on the activity because of the strong electronic donation to metallic Ru. Much higher activity can be obtained for Ru/AC catalyst with binary or triple promoters. The activity of Ru/AC catalyst is dependent on the adsorption of hydrogen and nitrogen. The high activity of catalyst could be ascribed to strong dissociation of nitrogen on the catalyst surface. Strong adsorption of hydrogen would inhibit the adsorption of nitrogen, resulted in decrease of the catalytic activity. Ru/AC catalyst promoted by Sm2O3 shows the best dispersion of metallic Ru, since the partly reduced SmOx on the surface modifies the morphology of active sites and favors the dispersion of metallic Ru. The activity of Ru/AC catalysts is in accordance to the corresponding amount of nitrogen chemisorption and the desorption activation energy of nitrogen. The desorption activation energy for nitrogen decreases in the order of Ru>Ru-Ba>Ru-Sm>Ru-Ba-Sm>Ru-K>Ru-K-Sm>Ru-K-Ba>Ru-K-Ba-Sm, just opposite to the order of catalytic activity, suggesting that the ammonia synthesis over Ru-based catalyst is controlled by the step of dissociation of nitrogen.
