Methanol steam reforming(MSR)represents a promising route for hydrogen production,leveraging the high energy density and liquid-phase storage advantages of methanol.Copper-based catalysts have become indispensable for...Methanol steam reforming(MSR)represents a promising route for hydrogen production,leveraging the high energy density and liquid-phase storage advantages of methanol.Copper-based catalysts have become indispensable for MSR due to their cost-effectiveness,exceptional catalytic activity,and tunable selectivity.However,persistent challenges such as thermal sintering,undesirable CO byproduct formation,diminished low-temperature reactivity,and long-term catalyst deactivation limit their broad industrial deployment.This review comprehensively examines the mechanistic pathways of MSR over Cu-based catalysts,with particular focus on differentiating catalyst formulations optimized for high-temperature(>200°C)versus low-temperature(<200°C)operation.It highlights the decisive influence of Cu nanoparticle size,electronic structure,and crystal structure on catalytic performance.Cutting-edge design strategies,including multi-element engineering,innovative synthesis techniques,and deactivation mitigation,are critically evaluated to elucidate mechanistic connections between atomic-scale structure and catalytic performance enhancement.Finally,industrial applications of commercial Cu/ZnO/Al_(2)O_(3)variants and their scalability challenges are discussed,alongside prospective strategies for catalyst innovation and engineering to advance next-generation hydrogen production.展开更多
The increasing need for efficient,sustainable,and environmentally friendly adsorbent materials has driven interest in bio-based alternatives.Conventional silica-based adsorbents,while effective,are often brittle and e...The increasing need for efficient,sustainable,and environmentally friendly adsorbent materials has driven interest in bio-based alternatives.Conventional silica-based adsorbents,while effective,are often brittle and energy-intensive to produce.In contrast,wood offers a renewable and low-energy option with natural porosity suitable for adsorption.This study investigated the fabrication of wood sponge from tropical balsa(Ochroma bicolor)and pulai(Alstonia scholaris)wood through a dual-stage delignification process as a novel bio-based adsorbent.The process involved alkaline treatment using sodium sulfite(Na_(2)SO_(3))and sodium hydroxide(NaOH)at 100℃for 8,9,and 10 h,followed by bleaching process using hydrogen peroxide(H_(2)O_(2))at 100℃for 1,2,and 3 h.The treated samples were then rinsed to neutral pH,frozen at−20℃for 24 h,and freeze-dried at−50℃for 48 h.The results revealed a notable reduction in density and specific gravity,accompanied by increased weight loss and pore diameter size with prolonged delignification process.Optical changes showed increased translucency and layered structures,particularly in balsa wood.FTIR analysis confirmed a reduction in lignin and hemicellulose content,validating the chemical modification within the treated samples.The resulting wood sponges exhibited good porosity and adsorption capacity,ranging from 1.3 to 5.7 g/g.The optimal treatment—10 h of alkaline delignification followed by 3 h of H_(2)O_(2)bleaching—demonstrated the highest performance,highlighting the potential of tropical wood species as efficient,biodegradable,and eco-friendly adsorbent materials.展开更多
Hospital wastewater contains complex pollutants,including residual organic dyes and antibiotic-resistant pathogens,posing severe risks to ecosystems and human health.Conventional adsorbents,constrained by monopolar fu...Hospital wastewater contains complex pollutants,including residual organic dyes and antibiotic-resistant pathogens,posing severe risks to ecosystems and human health.Conventional adsorbents,constrained by monopolar functional groups and limited surface sites,fail to remove both pollutants simultaneously.Here,we report an intelligent responsive polyurethane microsphere adsorbent doped with diallyl dimethylammonium chloride modified carbon nanotubes,termed as PUCD microspheres.The PUCD integrates bipolar adsorption sites,tunable micrometer-scale pores,and a near-infrared(NIR)-triggered in situ capture mechanism within a single platform,which achieves up to 98.3%dye removal,maintains strong adsorption performance across a wide pH range and retains 83.3%efficiency for rhodamine B after five cycles.Notably,the PUCD employs a temperature-responsive phase transition:under NIR irradiation,the microspheres undergo shrinkage,reducing the pore size to generate a‘polymer trap',enabling in situ capture of bacteria with>99%efficiencies for both Staphylococcus aureus and Escherichia coli.By immobilizing live bacteria,the PUCD microspheres substantially reduces the risk of pathogen desorption and toxin release.This promising platform offers a safe,efficient,and single-stage strategy for hospital wastewater purification,enabling the simultaneous elimination of dyes and pathogenic bacteria.展开更多
Currently,the solid adsorbents with porous structure have been widely applied in CO_(2)capture.However,the unmodified MgO-ZrO_(2)adsorbents appeared to be low adsorption capacity of CO_(2).The solid adsorbent material...Currently,the solid adsorbents with porous structure have been widely applied in CO_(2)capture.However,the unmodified MgO-ZrO_(2)adsorbents appeared to be low adsorption capacity of CO_(2).The solid adsorbent materials were successfully synthesized by loading TEPA onto the pore MgO/ZrO_(2)carriers in the paper.The pore structure and surface characteristic of the samples were analyzed by using XRD,BET,FT-IR and SEM.The adsorbent materials exhibited microcrystalline state,and the crystallinity of all samples gradually decreased as the increase of TEPA content.The pore structure analysis indicated that the modification of MgO-ZrO_(2)adsorbents with TEPA led to the decrease of the specific surface areas,but the narrow micro-mesopore size distributions ranging from 1.8-12 nm in the adsorbents still were maintained.FT-IR spectrum results further verified the successful loading of TEPA.The adsorption capacity of the adsorbents for CO_(2)were tested by using an adsorption apparatus equipped with gas chromatography.The results indicated that when the TEPA loading reached 50%,the sample exhibited the maximum adsorption value for CO_(2),reaching 4.07 mmol/g under the operation condition of 75℃and atmospheric pressure.This result could be assigned to not only the base active sites but also the coexistence of both micropore and mesopore in the adsorbent.After three cycles tests for CO_(2)capture,the adsorption value of the sample for CO_(2)can also reached 95%of its original adsorption capacity,which verified the excellent cyclic operation stability.展开更多
Conventional powder/pellet-based systems used for mitigating the environmental challenges posed by CO_(2)emissions present inefficiencies in mass/heat transfer,pressure drop,and clogging.Monolithic adsorption material...Conventional powder/pellet-based systems used for mitigating the environmental challenges posed by CO_(2)emissions present inefficiencies in mass/heat transfer,pressure drop,and clogging.Monolithic adsorption materials have emerged as a promising alternative to such systems.Additive manufacturing(AM)enables precise structural optimization and active component control in monolithic adsorbents,enhancing the adsorption kinetics while minimizing mechanical wear.This review examines the progress in AM-driven CO_(2)adsorbent development,covering the following aspects:(1)fabrication techniques for monolithic adsorbents and key metrics for evaluating their mechanical and adsorption properties,(2)applications of AM methods(extrusion,coating,gel spinning,and 3D printing)under fixed-source and direct-air capture scenarios,and(3)integrated systems combining CO_(2)adsorption and conversion.However,balancing adsorption performance with mechanical strength is a critical challenge.The trade-off can be addressed through advanced AM strategies such as hybrid material architectures and computational design.Future advancements will hinge on hybrid AM techniques to decouple structural and functional demands,AI/ML-driven multi-objective optimization for pore structure refinement and stress distribution,and lifecycle sustainability analytics to reduce energy use and material waste.By synergizing these approaches,next-generation monolithic adsorbents can achieve high capacity,mechanical robustness,and cost-effectiveness,positioning AM as a scalable and sustainable platform for carbon capture technologies.展开更多
Electrocatalytic carbon dioxide reduction(ECO_(2)RR)serves as a promising approach for converting CO_(2)into energy-dense fuels and high-value chemicals,garnering substantial interest across academic and industrial se...Electrocatalytic carbon dioxide reduction(ECO_(2)RR)serves as a promising approach for converting CO_(2)into energy-dense fuels and high-value chemicals,garnering substantial interest across academic and industrial sectors.Copper(Cu)-based electrocatalysts are widely acknowledged as highly effective for ECO_(2)RR,primarily due to their optimal adsorption energy for*CO.Nonetheless,significant challenges remain to be addressed in transitioning Cu-based catalysts from research settings to industrial applications,including the low stability and unavoidable side reactions.This article aims to i)systematically examine the deactivation mechanisms of Cu-based catalysts,including changes in valence states,surface poisoning,and restructuring(agglomeration,dissolution,Ostwald ripening);ii)provide a timely overview of cutting-edge strategies to enhance the stability of Cu-based catalysts,such as ligand effects,heteroatom doping,support optimization,size effect,and restructuring;iii)highlight critical areas and prospective development directions that warrant further exploration to expedite the industrial adoption of Cu-based catalysts in ECO_(2)RR.展开更多
The low stability of copper-based catalysts caused by dynamic reconstruction during the electrocatalytic CO_(2) reduction(ECR)process restricts their practical applications.Here,we developed a high performance Cu_(2)O...The low stability of copper-based catalysts caused by dynamic reconstruction during the electrocatalytic CO_(2) reduction(ECR)process restricts their practical applications.Here,we developed a high performance Cu_(2)O polycrystalline catalyst for the ECR,featuring enhanced stability and selectivity toward multi-carbon products.This is achieved through targeted grain boundary engineering(GBE)where the grain size and boundary density of the catalyst were manipulated via varying the concentrations of metal source and precipitant.The as-prepared catalyst with an optimal grain size and high boundary density demonstrated an excellent selectivity(>80%)toward multi-carbon products under ampere-level current density and a promising stability(~100 h)under industry-related conditions(200 mA cm^(-2)).By employing in situ and online characterization techniques,it was found that Cu_(2)O catalyst with moderate grain sizes exhibited the lowest dissolution and reconstruction rates during ECR resulting in significantly enhanced stability.Furthermore,a volcano-like relationship between the grain size and ECR stability was identified.The beneficial impacts of concave grain boundaries on the stability of Cu-based catalysts were evidenced,and insights into the molecular interactions at play as well as the origin of the observed volcano-like relationship were obtained by density functional theory(DFT)calculations.展开更多
This study introduced a microwave-assisted pyrolysis method for the rapid and efficientpreparation of boron-doped porous biochar. The resulting biochar exhibited a large specificsurface area (933.39 m^(2)/g), a rich p...This study introduced a microwave-assisted pyrolysis method for the rapid and efficientpreparation of boron-doped porous biochar. The resulting biochar exhibited a large specificsurface area (933.39 m^(2)/g), a rich porous structure (1.044 cm3/g), and abundant active sites.Consequently, the prepared boron-doped porous biochar exhibited higher efficiency in adsorbingtetracycline with a maximum adsorption capacity of 413.223 mg/g, which significantlyexceeded that of unmodified biochar andmost commercial and reported adsorbents.The correlation analysis between the adsorption capacity and adsorbent characteristics revealedthat the formation of the –BCO_(2) group enhanced π–π electron donor–acceptor interactionsbetween boron-doped porous biochar and tetracycline. This mechanism mainlycontributed to the enhanced adsorption of tetracycline by boron-doped porous biochar. Additionally,the as-prepared boron-doped porous biochar exhibited broad applications in removingantibiotics (tetracycline), phenolics (bisphenol A), and dyes (methylene blue andrhodamine B). Moreover, the boron-doped porous biochar exhibited satisfactory stability,and its adsorption capacity can be nearly completely regenerated through simple heat treatment.This study provides new insights into the effectiveness of boron-doped carbonaceousmaterials in removing antibiotic contaminants.展开更多
Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low r...Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.展开更多
Geological samples often contain significant amounts of iron,which,although not typically the target element,can substantially interfere with the analysis of other elements of interest.To mitigate these interferences,...Geological samples often contain significant amounts of iron,which,although not typically the target element,can substantially interfere with the analysis of other elements of interest.To mitigate these interferences,amidoximebased radiation grafted adsorbents have been identified as effective for iron removal.In this study,an amidoximefunctionalized,radiation-grafted adsorbent synthesized from polypropylene waste(PPw-g-AO-10)was employed to remove iron from leached geological samples.The adsorption process was systematically optimized by investigating the effects of pH,contact time,adsorbent dosage,and initial ferric ion concentration.Under optimal conditions-pH1.4,a contact time of 90 min,and an initial ferric ion concentration of 4500 mg/L-the adsorbent exhibited a maximum iron adsorption capacity of 269.02 mg/g.After optimizing the critical adsorption parameters,the adsorbent was applied to the leached geological samples,achieving a 91%removal of the iron content.The adsorbent was regenerated through two consecutive cycles using 0.2 N HNO_(3),achieving a regeneration efficiency of 65%.These findings confirm the efficacy of the synthesized PPw-g-AO-10 as a cost-effective and eco-friendly adsorbent for successfully removing iron from leached geological matrices while maintaining a reasonable degree of reusability.展开更多
Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance ...Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance of various catalysts by tuning their oxidation states,particularly for Cu-based catalysts that can reduce CO_(2) to multiple products.However,the oxidation state of copper(OSCu),especially Cu+,changes during the reaction process,posing significant challenges for both catalyst characterization and performance.In this review,the current understanding of the effect of oxidation states on product selectivity was first discussed.A comprehensive overview of in situ/operando characterization techniques,used to monitor the dynamic evolution of oxidation states during ECR,was then provided.Various strategies for stabilizing oxidation states through modification of catalysts and manipulation of external conditions were discussed.This review aimed to deepen the understanding of oxidation states in ECR and enlighten the development of more efficient electrocatalysts.展开更多
Global investment in ethylene(C_(2)H_(4))production via nonpetroleum pathways is rising,highlighting its growing importance in the energy and environmental sectors.The electroreduction of carbon dioxide(CO_(2))to C_(2...Global investment in ethylene(C_(2)H_(4))production via nonpetroleum pathways is rising,highlighting its growing importance in the energy and environmental sectors.The electroreduction of carbon dioxide(CO_(2))to C_(2)H_(4) inflow cells is emerging as a promising technology with broad practical applications.Direct delivery of gaseous CO_(2) to the cathode catalyst layer overcomes mass transfer limitations,enhancing reaction rates and enabling high current density.This review summarizes recent research progress in the electrocatalytic CO_(2) reduction reaction(eCO_(2)RR)for selective C_(2)H_(4) production inflow cells.It outlines the principles of eCO_(2)RR to C_(2)H_(4) and discusses the influence of copper-based catalyst morphology,crystal facet,oxidation state,surface modification strategy,and synergistic effects on catalytic performance.In addition,it highlights the compositional structure of theflow cell,and the selection and optimization of operating conditions,including gas diffusion electrodes,electrolytes,ion exchange membranes,and alternative anode reaction types beyond the oxygen evolution reaction.Finally,advances in machine learning are presented for accelerating catalyst screening and predicting dynamic changes in catalysts during reduction.This comprehensive review serves as a valuable reference for the development of efficient catalysts and the construction of electrolytic devices for the electrocatalytic reduction of CO_(2) to C_(2)H_(4).展开更多
Dual atomic catalysts(DAC),particularly copper(Cu_(2))-based nitrogen(N)doped graphene,show great potential to effectively convert CO_(2)and nitrate(NO_(3)-)into important industrial chemicals such as ethylene,glycol,...Dual atomic catalysts(DAC),particularly copper(Cu_(2))-based nitrogen(N)doped graphene,show great potential to effectively convert CO_(2)and nitrate(NO_(3)-)into important industrial chemicals such as ethylene,glycol,acetamide,and urea through an efficient catalytical process that involves C–C and C–N coupling.However,the origin of the coupling activity remained unclear,which substantially hinders the rational design of Cu-based catalysts for the N-integrated CO_(2)reduction reaction(CO_(2)RR).To address this challenge,this work performed advanced density functional theory calculations incorporating explicit solvation based on a Cu_(2)-based N-doped carbon(Cu_(2)N_(6)C_(10))catalyst for CO_(2)RR.These calculations are aimed to gain insight into the reaction mechanisms for the synthesis of ethylene,acetamide,and urea via coupling in the interfacial reaction micro-environment.Due to the sluggishness of CO_(2),the formation of a solvation electric layer by anions(F^(-),Cl^(-),Br^(-),and I^(-))and cations(Na+,Mg^(2+),K+,and Ca^(2+))leads to electron transfer towards the Cu surface.This process significantly accelerates the reduction of CO_(2).These results reveal that*CO intermediates play a pivotal role in N-integrated CO_(2)RR.Remarkably,the Cu_(2)-based N-doped carbon catalyst examined in this study has demonstrated the most potential for C–N coupling to date.Our findings reveal that through the process of a condensation reaction between*CO and NH_(2)OH for urea synthesis,*NO_(3)-is reduced to*NH_(3),and*CO_(2)to*CCO at dual Cu atom sites.This dual-site reduction facilitates the synthesis of acetamide through a nucleophilic reaction between NH_(3)and the ketene intermediate.Furthermore,we found that the I-and Mg^(2+)ions,influenced by pH,were highly effective for acetamide and ammonia synthesis,except when F-and Ca^(2+)were present.Furthermore,the mechanisms of C–N bond formation were investigated via ab-initio molecular dynamics simulations,and we found that adjusting the micro-environment can change the dominant side reaction,shifting from hydrogen production in acidic conditions to water reduction in alkaline ones.This study introduces a novel approach using ion-H_(2)O cages to significantly enhance the efficiency of C–N coupling reactions.展开更多
Although supported solid amine adsorbents have attracted great attention for CO_(2) capture,critical chemical deactivation problems including oxidative degradation and urea formation have severely restricted their pra...Although supported solid amine adsorbents have attracted great attention for CO_(2) capture,critical chemical deactivation problems including oxidative degradation and urea formation have severely restricted their practical applications for flue gas CO_(2) capture.In this work,we reveal that the nature of surface hydroxyl groups(metal hydroxyl Al–OH and nonmetal hydroxyl Si–OH)plays a key role in the deactivation mechanisms.The polyethyleneimine(PEI)supported on Al–OH-containing substrates suffers from severe oxidative degradation during the CO_(2) capture step due to the breakage of amine-support hydrogen bonding networks,but exhibits an excellent anti-urea formation feature by preventing dehydration of carbamate products under a pure CO_(2) regeneration atmosphere.In contrast,PEI supported on Si–OHcontaining substrates exhibits excellent anti-oxidative stability under simulated flue gas conditions by forming a robust hydrogen bonding protective network with Si–OH,but suffers from obvious urea formation during the pure CO_(2) regeneration step.We also reveal that the urea formation problem for PEI-SBA-15 can be avoided by the incorporation of an OH-containing PEG additive.Based on the intrinsic understanding of degradation mechanisms,we successfully synthesized an adsorbent 40PEI-20PEG-SBA-15 that demonstrates outstanding stability and retention of a high CO_(2) capacity of 2.45 mmol g^(−1) over 1000 adsorption–desorption cycles,together with negligible capacity loss during aging in simulated flue gas(10%CO_(2)+5%O_(2)+3%H_(2)O)for one month at 60–70℃.We believe this work makes great contribution to the advancement in the field of ultra-stable solid amine-based CO_(2) capture materials.展开更多
Desulfurization technology is rather difficult and urgently needed for carbon dioxide(CO_(2))utilization in industry.A new Cu(I)-based adsorbent was synthesized and examined for the capacity of removing carbonyl sulfi...Desulfurization technology is rather difficult and urgently needed for carbon dioxide(CO_(2))utilization in industry.A new Cu(I)-based adsorbent was synthesized and examined for the capacity of removing carbonyl sulfide(COS)from a CO_(2)stream in an effort to solve the competitive adsorption between CO_(2)and COS and to seek opportunity to advance adsorption capacity.A wide range of character-ization techniques were used to investigate the physicochemical properties of the synthesized Cu(I)adsorbent featuringπ-complexation and their correlations with the adsorption performance.Meanwhile,the first principal calculation software CP2K was used to develop an understanding of the adsorption mechanism,which can offer useful guidance for the adsorbent regeneration.The synthesized Cu(I)adsorbent,prepared by using copper citrate and citric acid on the ZSM-5(SiO_(2)/Al_(2)O_(3)=25)carrier,outperformed other adsorbents with varying formulations and carriers in adsorption capacities.Through optimization of the preparation and adsorption conditions for various adsorbents,the breakthrough adsorption capacity(Qb)for COS was further enhanced from 2.19 mg/g to 15.36 mg/g.The formed stableπ-complex bonds between COS and Cu(I),as confirmed by density func-tional theory calculations,were verified by the significant improvement in the adsorption capacity after regeneration at 600°C.The above advantages render the novel synthesized Cu(I)adsorbent a promising candidate featuring cost-effectiveness,high efficacy and good regenerability for desulfurization from a CO_(2)stream.展开更多
Sodium-based adsorbents(Na_(2)CO_(3)/γ-Al_(2)O_(3))exhibit significant potential for commercial utilization in CO_(2)capture.Nevertheless,the requirement for high desorption temperatures poses challenges in terms of ...Sodium-based adsorbents(Na_(2)CO_(3)/γ-Al_(2)O_(3))exhibit significant potential for commercial utilization in CO_(2)capture.Nevertheless,the requirement for high desorption temperatures poses challenges in terms of the high-quality heat needed for desorption.This study integrated ZrO_(2)doping into a sodium-based adsorbent to enhance its CO_(2)capture performance and lower its desorption temperature.The research investigated the CO_(2)adsorption capacity,reaction rate,and desorption characteristics of the ZrO_(2)-doped Na_(2)CO_(3)/γ-Al_(2)O_(3)adsorbents in detail.Additionally,the catalytic mechanism of ZrO_(2)was elucidated through Density Functional Theory calculations.The results showed that ZrO_(2)doping increased the adsorption rate and capacity of the adsorbent and reduced the desorption energy consumption.Desorption reaction activation energy reduced to 44.8 kJ/mol.The adsorbent doped with 3wt.%ZrO_(2)demonstrated the highest adsorption capacity and rate under optimal conditions,with a reaction temperature of 45℃,an adsorption capacity of 1.66 mmol/g,and a carbon conversion rate of 80.2%.ZrO_(2)acted as a catalyst,enhancing CO_(2)and H_(2)O adsorption,and facilitated CO_(2)desorption in the sodium-based adsorbent by forming[ZrO(OH)]^(+)and OH^(−)through H_(2)O adsorption activation.The lower energy barrier(0.17 eV)for the dissociative adsorption pathway of H_(2)O molecules on the ZrO_(2)surface further supported the role of ZrO_(2)in enhancing the overall adsorption performance of the adsorbent in the carbon capture process.Ultimately,the ZrO_(2)-doped Na_(2)CO_(3)/γ-Al_(2)O_(3)adsorbent was identified as having low desorption energy consumption,high adsorption capacity,and rate,offering potential cost reductions in CO_(2)capture and representing a promising adsorbent for this application.展开更多
Density functional theory(DFT)has helped propel the advance of electrocatalysis in the past two decades.In view of its massive use,it is worth asking how reliable DFT is for the prediction of adsorption energies,which...Density functional theory(DFT)has helped propel the advance of electrocatalysis in the past two decades.In view of its massive use,it is worth asking how reliable DFT is for the prediction of adsorption energies,which are paramount in computational electrocatalysis models.Here,we provide an experimental-computational approach to break down overall adsorption-energy errors into separate gas-phase and adsorbed-phase contributions.The method is evaluated using experimental data and various exchange-correlation functionals and materials for C-and O-containing species.Our main conclusion is that no functional is simultaneously accurate for adsorbates and molecules,as adsorbed-phase errors are visibly different from gas-phase errors.Importantly,total,gas-phase,and adsorbed-phase errors are correlated,revealing intrinsic DFT limitations and enabling the elaboration of swift correction routines.To illustrate the benefits of our approach,we deconvolute and correct all errors in CO_(2)electroreduction to CO and find an agreement with experiments close to chemical accuracy for numerous transition-metal electrodes and all scrutinized functionals.展开更多
A series of copper-based activated carbon (AC) adsorbents were prepared in order to investigate the effect of Zn, Ce addition on Cu-based AC adsorbent for phosphine (PH3) adsorption removal from yellow phosphorous tai...A series of copper-based activated carbon (AC) adsorbents were prepared in order to investigate the effect of Zn, Ce addition on Cu-based AC adsorbent for phosphine (PH3) adsorption removal from yellow phosphorous tail gas. N2 adsorption isotherm and X-ray diffrac-tion (XRD) results suggested that the addition of Zn could increase the adsorbent ultramicropores, decrease the adsorbent supermicropores and the adsorbent average pore diameter. Therefore it enhanced the PH3 adsorption capacity. Appropriate amoun...展开更多
Bulk Cu50Zr40Ti10 amorphous alloy composites reinforced with carbon nanotube （CNT） were successfully fabricated by hot pressing technique. Their density, thermal conductivity, and mechanical properties were systemic...Bulk Cu50Zr40Ti10 amorphous alloy composites reinforced with carbon nanotube （CNT） were successfully fabricated by hot pressing technique. Their density, thermal conductivity, and mechanical properties were systemically investigated. The density and the compression strength of the compacts both decrease with increasing CNT content. The thermal conductivity of the compacts decreases when the CNT content is less than 0.10% or exceeds 0.60% （mass fraction）, while increases when the CNT content is in the range of 0.1%-0.6%. The strain limit and the modulus of the compacts are obviously improved when the CNT content is less than 1.0% and then decrease significantly when the CNT content exceeds 1.00%. The optimum CNT addition is less than 0.20% at the comprehensive properties point of view.展开更多
H2TiO3 was obtained from the acid-modified adsorbent precursor Li2TiO3,which was synthesized by a solid-phase reaction between TiO2 and Li2CO3.The extraction ratio of Li＋ from Li2TiO3 was 98.86%,almost with no Ti4＋ ...H2TiO3 was obtained from the acid-modified adsorbent precursor Li2TiO3,which was synthesized by a solid-phase reaction between TiO2 and Li2CO3.The extraction ratio of Li＋ from Li2TiO3 was 98.86%,almost with no Ti4＋ extracted.The effects of lithium titanium ratio,calcining temperature and time were investigated on the synthesis of Li2TiO3.Li2TiO3,H2TiO3 and the adsorbed Li＋ adsorbent were characterized by XRD and SEM.The lithium adsorption properties were investigated by the adsorption kinetics and adsorption isotherm.The results indicate that H2TiO3 has an excellent adsorptive capacity for Li＋.Two simplified kinetic models including the pseudo-first-order and pseudo-second-order equations were selected to follow the adsorption processes.The rate constants of adsorption for these kinetic models were calculated.The results show that the adsorption process can be described by the pseudo-second-order equation,and the process is proved to be a chemical adsorption.The adsorption process that H2TiO3 adsorbs Li＋ in LiCl solution well fits the Langmuir equation with monolayer adsorption.展开更多
基金supported by the National Natural Science Foundation of China(No.22208374)the Excellent Youth Scientist Award Foundation of Shandong Province(No.ZR2024YQ009)+2 种基金the Distinguished Young Scholars of the National Natural Science Foundation of China(No.22322814)CNPC Innovation Found(2022DQ02-0607)the Fundamental Research Funds for the Central Universities(No.24CX07006A).
文摘Methanol steam reforming(MSR)represents a promising route for hydrogen production,leveraging the high energy density and liquid-phase storage advantages of methanol.Copper-based catalysts have become indispensable for MSR due to their cost-effectiveness,exceptional catalytic activity,and tunable selectivity.However,persistent challenges such as thermal sintering,undesirable CO byproduct formation,diminished low-temperature reactivity,and long-term catalyst deactivation limit their broad industrial deployment.This review comprehensively examines the mechanistic pathways of MSR over Cu-based catalysts,with particular focus on differentiating catalyst formulations optimized for high-temperature(>200°C)versus low-temperature(<200°C)operation.It highlights the decisive influence of Cu nanoparticle size,electronic structure,and crystal structure on catalytic performance.Cutting-edge design strategies,including multi-element engineering,innovative synthesis techniques,and deactivation mitigation,are critically evaluated to elucidate mechanistic connections between atomic-scale structure and catalytic performance enhancement.Finally,industrial applications of commercial Cu/ZnO/Al_(2)O_(3)variants and their scalability challenges are discussed,alongside prospective strategies for catalyst innovation and engineering to advance next-generation hydrogen production.
基金This work was supported by Riset dan Inovasi untuk Indonesia Maju(RIIM)Kompetisi scheme(Grant number:48/II.7/HK/2025)RP ORNM 2025,National Collaborative Research/RiNa(No.499/2023)Penelitian Dosen Pemula grant from the Ministry of Higher Education,Science and Technology,Republic of Indonesia(1483az/IT9.2.1/PT.01.03/2025).
文摘The increasing need for efficient,sustainable,and environmentally friendly adsorbent materials has driven interest in bio-based alternatives.Conventional silica-based adsorbents,while effective,are often brittle and energy-intensive to produce.In contrast,wood offers a renewable and low-energy option with natural porosity suitable for adsorption.This study investigated the fabrication of wood sponge from tropical balsa(Ochroma bicolor)and pulai(Alstonia scholaris)wood through a dual-stage delignification process as a novel bio-based adsorbent.The process involved alkaline treatment using sodium sulfite(Na_(2)SO_(3))and sodium hydroxide(NaOH)at 100℃for 8,9,and 10 h,followed by bleaching process using hydrogen peroxide(H_(2)O_(2))at 100℃for 1,2,and 3 h.The treated samples were then rinsed to neutral pH,frozen at−20℃for 24 h,and freeze-dried at−50℃for 48 h.The results revealed a notable reduction in density and specific gravity,accompanied by increased weight loss and pore diameter size with prolonged delignification process.Optical changes showed increased translucency and layered structures,particularly in balsa wood.FTIR analysis confirmed a reduction in lignin and hemicellulose content,validating the chemical modification within the treated samples.The resulting wood sponges exhibited good porosity and adsorption capacity,ranging from 1.3 to 5.7 g/g.The optimal treatment—10 h of alkaline delignification followed by 3 h of H_(2)O_(2)bleaching—demonstrated the highest performance,highlighting the potential of tropical wood species as efficient,biodegradable,and eco-friendly adsorbent materials.
基金financially supported by the National Natural Science Foundation of China(Nos.52473139 and U21A2098)。
文摘Hospital wastewater contains complex pollutants,including residual organic dyes and antibiotic-resistant pathogens,posing severe risks to ecosystems and human health.Conventional adsorbents,constrained by monopolar functional groups and limited surface sites,fail to remove both pollutants simultaneously.Here,we report an intelligent responsive polyurethane microsphere adsorbent doped with diallyl dimethylammonium chloride modified carbon nanotubes,termed as PUCD microspheres.The PUCD integrates bipolar adsorption sites,tunable micrometer-scale pores,and a near-infrared(NIR)-triggered in situ capture mechanism within a single platform,which achieves up to 98.3%dye removal,maintains strong adsorption performance across a wide pH range and retains 83.3%efficiency for rhodamine B after five cycles.Notably,the PUCD employs a temperature-responsive phase transition:under NIR irradiation,the microspheres undergo shrinkage,reducing the pore size to generate a‘polymer trap',enabling in situ capture of bacteria with>99%efficiencies for both Staphylococcus aureus and Escherichia coli.By immobilizing live bacteria,the PUCD microspheres substantially reduces the risk of pathogen desorption and toxin release.This promising platform offers a safe,efficient,and single-stage strategy for hospital wastewater purification,enabling the simultaneous elimination of dyes and pathogenic bacteria.
基金supported by Shanxi Provincial Key Research and Development Project(202102090301026)Graduate Education Innovation Project of Taiyuan University of Science and Technology(SY2023024)。
文摘Currently,the solid adsorbents with porous structure have been widely applied in CO_(2)capture.However,the unmodified MgO-ZrO_(2)adsorbents appeared to be low adsorption capacity of CO_(2).The solid adsorbent materials were successfully synthesized by loading TEPA onto the pore MgO/ZrO_(2)carriers in the paper.The pore structure and surface characteristic of the samples were analyzed by using XRD,BET,FT-IR and SEM.The adsorbent materials exhibited microcrystalline state,and the crystallinity of all samples gradually decreased as the increase of TEPA content.The pore structure analysis indicated that the modification of MgO-ZrO_(2)adsorbents with TEPA led to the decrease of the specific surface areas,but the narrow micro-mesopore size distributions ranging from 1.8-12 nm in the adsorbents still were maintained.FT-IR spectrum results further verified the successful loading of TEPA.The adsorption capacity of the adsorbents for CO_(2)were tested by using an adsorption apparatus equipped with gas chromatography.The results indicated that when the TEPA loading reached 50%,the sample exhibited the maximum adsorption value for CO_(2),reaching 4.07 mmol/g under the operation condition of 75℃and atmospheric pressure.This result could be assigned to not only the base active sites but also the coexistence of both micropore and mesopore in the adsorbent.After three cycles tests for CO_(2)capture,the adsorption value of the sample for CO_(2)can also reached 95%of its original adsorption capacity,which verified the excellent cyclic operation stability.
基金supported by National Natural Science Foundation of China(Grant Nos.52476223,22038011)the Programme of Introducing Talents of Discipline to Universities(Grant No.B23025)+1 种基金K.C.Wong Education Foundation,Fundamental Research Funds for the Central Universities(Grant No.xzy012023074)the Innovation Capability Support Program of Shaanxi(Grant Nos.2023KJKXX-004,2022KXJ-126).
文摘Conventional powder/pellet-based systems used for mitigating the environmental challenges posed by CO_(2)emissions present inefficiencies in mass/heat transfer,pressure drop,and clogging.Monolithic adsorption materials have emerged as a promising alternative to such systems.Additive manufacturing(AM)enables precise structural optimization and active component control in monolithic adsorbents,enhancing the adsorption kinetics while minimizing mechanical wear.This review examines the progress in AM-driven CO_(2)adsorbent development,covering the following aspects:(1)fabrication techniques for monolithic adsorbents and key metrics for evaluating their mechanical and adsorption properties,(2)applications of AM methods(extrusion,coating,gel spinning,and 3D printing)under fixed-source and direct-air capture scenarios,and(3)integrated systems combining CO_(2)adsorption and conversion.However,balancing adsorption performance with mechanical strength is a critical challenge.The trade-off can be addressed through advanced AM strategies such as hybrid material architectures and computational design.Future advancements will hinge on hybrid AM techniques to decouple structural and functional demands,AI/ML-driven multi-objective optimization for pore structure refinement and stress distribution,and lifecycle sustainability analytics to reduce energy use and material waste.By synergizing these approaches,next-generation monolithic adsorbents can achieve high capacity,mechanical robustness,and cost-effectiveness,positioning AM as a scalable and sustainable platform for carbon capture technologies.
基金support from the Technology Project of the State Grid Zhejiang Electric Power Company,Ltd.(No.B311DS230005).
文摘Electrocatalytic carbon dioxide reduction(ECO_(2)RR)serves as a promising approach for converting CO_(2)into energy-dense fuels and high-value chemicals,garnering substantial interest across academic and industrial sectors.Copper(Cu)-based electrocatalysts are widely acknowledged as highly effective for ECO_(2)RR,primarily due to their optimal adsorption energy for*CO.Nonetheless,significant challenges remain to be addressed in transitioning Cu-based catalysts from research settings to industrial applications,including the low stability and unavoidable side reactions.This article aims to i)systematically examine the deactivation mechanisms of Cu-based catalysts,including changes in valence states,surface poisoning,and restructuring(agglomeration,dissolution,Ostwald ripening);ii)provide a timely overview of cutting-edge strategies to enhance the stability of Cu-based catalysts,such as ligand effects,heteroatom doping,support optimization,size effect,and restructuring;iii)highlight critical areas and prospective development directions that warrant further exploration to expedite the industrial adoption of Cu-based catalysts in ECO_(2)RR.
基金supported by research grants from China Petrochemical Corporation(Grants 223061 and 224125)support from the UK EPSRC(EP/W03784X/1).
文摘The low stability of copper-based catalysts caused by dynamic reconstruction during the electrocatalytic CO_(2) reduction(ECR)process restricts their practical applications.Here,we developed a high performance Cu_(2)O polycrystalline catalyst for the ECR,featuring enhanced stability and selectivity toward multi-carbon products.This is achieved through targeted grain boundary engineering(GBE)where the grain size and boundary density of the catalyst were manipulated via varying the concentrations of metal source and precipitant.The as-prepared catalyst with an optimal grain size and high boundary density demonstrated an excellent selectivity(>80%)toward multi-carbon products under ampere-level current density and a promising stability(~100 h)under industry-related conditions(200 mA cm^(-2)).By employing in situ and online characterization techniques,it was found that Cu_(2)O catalyst with moderate grain sizes exhibited the lowest dissolution and reconstruction rates during ECR resulting in significantly enhanced stability.Furthermore,a volcano-like relationship between the grain size and ECR stability was identified.The beneficial impacts of concave grain boundaries on the stability of Cu-based catalysts were evidenced,and insights into the molecular interactions at play as well as the origin of the observed volcano-like relationship were obtained by density functional theory(DFT)calculations.
基金supported by the National Natural Science Foundation of China(Nos.52100062,and 52230001)China Postdoctoral Science Foundation(No.2023M732785).
文摘This study introduced a microwave-assisted pyrolysis method for the rapid and efficientpreparation of boron-doped porous biochar. The resulting biochar exhibited a large specificsurface area (933.39 m^(2)/g), a rich porous structure (1.044 cm3/g), and abundant active sites.Consequently, the prepared boron-doped porous biochar exhibited higher efficiency in adsorbingtetracycline with a maximum adsorption capacity of 413.223 mg/g, which significantlyexceeded that of unmodified biochar andmost commercial and reported adsorbents.The correlation analysis between the adsorption capacity and adsorbent characteristics revealedthat the formation of the –BCO_(2) group enhanced π–π electron donor–acceptor interactionsbetween boron-doped porous biochar and tetracycline. This mechanism mainlycontributed to the enhanced adsorption of tetracycline by boron-doped porous biochar. Additionally,the as-prepared boron-doped porous biochar exhibited broad applications in removingantibiotics (tetracycline), phenolics (bisphenol A), and dyes (methylene blue andrhodamine B). Moreover, the boron-doped porous biochar exhibited satisfactory stability,and its adsorption capacity can be nearly completely regenerated through simple heat treatment.This study provides new insights into the effectiveness of boron-doped carbonaceousmaterials in removing antibiotic contaminants.
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.
文摘Geological samples often contain significant amounts of iron,which,although not typically the target element,can substantially interfere with the analysis of other elements of interest.To mitigate these interferences,amidoximebased radiation grafted adsorbents have been identified as effective for iron removal.In this study,an amidoximefunctionalized,radiation-grafted adsorbent synthesized from polypropylene waste(PPw-g-AO-10)was employed to remove iron from leached geological samples.The adsorption process was systematically optimized by investigating the effects of pH,contact time,adsorbent dosage,and initial ferric ion concentration.Under optimal conditions-pH1.4,a contact time of 90 min,and an initial ferric ion concentration of 4500 mg/L-the adsorbent exhibited a maximum iron adsorption capacity of 269.02 mg/g.After optimizing the critical adsorption parameters,the adsorbent was applied to the leached geological samples,achieving a 91%removal of the iron content.The adsorbent was regenerated through two consecutive cycles using 0.2 N HNO_(3),achieving a regeneration efficiency of 65%.These findings confirm the efficacy of the synthesized PPw-g-AO-10 as a cost-effective and eco-friendly adsorbent for successfully removing iron from leached geological matrices while maintaining a reasonable degree of reusability.
基金supported by the National Natural Science Foundation of China(No.52221004)the Shenzhen Science and Technology Program(No.RCJC20221008092758099)+1 种基金the Shenzhen Pengrui Young Faculty Program of Shenzhen Pengrui Foundation(No.SZPR2023004)the Guangdong Higher Education Institutions Innovative Research Team of Urban Water Cycle and Ecological Safety(No.2023KCXTD053).
文摘Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance of various catalysts by tuning their oxidation states,particularly for Cu-based catalysts that can reduce CO_(2) to multiple products.However,the oxidation state of copper(OSCu),especially Cu+,changes during the reaction process,posing significant challenges for both catalyst characterization and performance.In this review,the current understanding of the effect of oxidation states on product selectivity was first discussed.A comprehensive overview of in situ/operando characterization techniques,used to monitor the dynamic evolution of oxidation states during ECR,was then provided.Various strategies for stabilizing oxidation states through modification of catalysts and manipulation of external conditions were discussed.This review aimed to deepen the understanding of oxidation states in ECR and enlighten the development of more efficient electrocatalysts.
基金supported by the National Natural Science Foundation of China(22272081 and 51802160)the Startup Foundation for Introducing Talent of NUIST(S8113082001).
文摘Global investment in ethylene(C_(2)H_(4))production via nonpetroleum pathways is rising,highlighting its growing importance in the energy and environmental sectors.The electroreduction of carbon dioxide(CO_(2))to C_(2)H_(4) inflow cells is emerging as a promising technology with broad practical applications.Direct delivery of gaseous CO_(2) to the cathode catalyst layer overcomes mass transfer limitations,enhancing reaction rates and enabling high current density.This review summarizes recent research progress in the electrocatalytic CO_(2) reduction reaction(eCO_(2)RR)for selective C_(2)H_(4) production inflow cells.It outlines the principles of eCO_(2)RR to C_(2)H_(4) and discusses the influence of copper-based catalyst morphology,crystal facet,oxidation state,surface modification strategy,and synergistic effects on catalytic performance.In addition,it highlights the compositional structure of theflow cell,and the selection and optimization of operating conditions,including gas diffusion electrodes,electrolytes,ion exchange membranes,and alternative anode reaction types beyond the oxygen evolution reaction.Finally,advances in machine learning are presented for accelerating catalyst screening and predicting dynamic changes in catalysts during reduction.This comprehensive review serves as a valuable reference for the development of efficient catalysts and the construction of electrolytic devices for the electrocatalytic reduction of CO_(2) to C_(2)H_(4).
基金National Natural Science Foundation of China(U22B20149,22308376)Outstanding Young Scholars Foundation of China University of Petroleum(Beijing)(2462023BJRC015)Foundation of United Institute for Carbon Neutrality(CNIF20230209)。
文摘Dual atomic catalysts(DAC),particularly copper(Cu_(2))-based nitrogen(N)doped graphene,show great potential to effectively convert CO_(2)and nitrate(NO_(3)-)into important industrial chemicals such as ethylene,glycol,acetamide,and urea through an efficient catalytical process that involves C–C and C–N coupling.However,the origin of the coupling activity remained unclear,which substantially hinders the rational design of Cu-based catalysts for the N-integrated CO_(2)reduction reaction(CO_(2)RR).To address this challenge,this work performed advanced density functional theory calculations incorporating explicit solvation based on a Cu_(2)-based N-doped carbon(Cu_(2)N_(6)C_(10))catalyst for CO_(2)RR.These calculations are aimed to gain insight into the reaction mechanisms for the synthesis of ethylene,acetamide,and urea via coupling in the interfacial reaction micro-environment.Due to the sluggishness of CO_(2),the formation of a solvation electric layer by anions(F^(-),Cl^(-),Br^(-),and I^(-))and cations(Na+,Mg^(2+),K+,and Ca^(2+))leads to electron transfer towards the Cu surface.This process significantly accelerates the reduction of CO_(2).These results reveal that*CO intermediates play a pivotal role in N-integrated CO_(2)RR.Remarkably,the Cu_(2)-based N-doped carbon catalyst examined in this study has demonstrated the most potential for C–N coupling to date.Our findings reveal that through the process of a condensation reaction between*CO and NH_(2)OH for urea synthesis,*NO_(3)-is reduced to*NH_(3),and*CO_(2)to*CCO at dual Cu atom sites.This dual-site reduction facilitates the synthesis of acetamide through a nucleophilic reaction between NH_(3)and the ketene intermediate.Furthermore,we found that the I-and Mg^(2+)ions,influenced by pH,were highly effective for acetamide and ammonia synthesis,except when F-and Ca^(2+)were present.Furthermore,the mechanisms of C–N bond formation were investigated via ab-initio molecular dynamics simulations,and we found that adjusting the micro-environment can change the dominant side reaction,shifting from hydrogen production in acidic conditions to water reduction in alkaline ones.This study introduces a novel approach using ion-H_(2)O cages to significantly enhance the efficiency of C–N coupling reactions.
基金supported by the Fundamental Research Funds for the National Natural Science Foundation of China 52225003,22208021,22109004the National Key R&D Program of China 2022YFB4101702.
文摘Although supported solid amine adsorbents have attracted great attention for CO_(2) capture,critical chemical deactivation problems including oxidative degradation and urea formation have severely restricted their practical applications for flue gas CO_(2) capture.In this work,we reveal that the nature of surface hydroxyl groups(metal hydroxyl Al–OH and nonmetal hydroxyl Si–OH)plays a key role in the deactivation mechanisms.The polyethyleneimine(PEI)supported on Al–OH-containing substrates suffers from severe oxidative degradation during the CO_(2) capture step due to the breakage of amine-support hydrogen bonding networks,but exhibits an excellent anti-urea formation feature by preventing dehydration of carbamate products under a pure CO_(2) regeneration atmosphere.In contrast,PEI supported on Si–OHcontaining substrates exhibits excellent anti-oxidative stability under simulated flue gas conditions by forming a robust hydrogen bonding protective network with Si–OH,but suffers from obvious urea formation during the pure CO_(2) regeneration step.We also reveal that the urea formation problem for PEI-SBA-15 can be avoided by the incorporation of an OH-containing PEG additive.Based on the intrinsic understanding of degradation mechanisms,we successfully synthesized an adsorbent 40PEI-20PEG-SBA-15 that demonstrates outstanding stability and retention of a high CO_(2) capacity of 2.45 mmol g^(−1) over 1000 adsorption–desorption cycles,together with negligible capacity loss during aging in simulated flue gas(10%CO_(2)+5%O_(2)+3%H_(2)O)for one month at 60–70℃.We believe this work makes great contribution to the advancement in the field of ultra-stable solid amine-based CO_(2) capture materials.
基金supported by the National Key Research and Development Program of China(2022YFA1504402)National Energy R&D Center of Petroleum Refining Technology(RIPP,SINOPEC)+2 种基金the National Natural Science Foundation of China(22472016 and U23B20169)Key R&D Program of Ningbo(No.2023Z144)the Fundamental Research Funds for the Central Universities(DUT22LAB601).
文摘Desulfurization technology is rather difficult and urgently needed for carbon dioxide(CO_(2))utilization in industry.A new Cu(I)-based adsorbent was synthesized and examined for the capacity of removing carbonyl sulfide(COS)from a CO_(2)stream in an effort to solve the competitive adsorption between CO_(2)and COS and to seek opportunity to advance adsorption capacity.A wide range of character-ization techniques were used to investigate the physicochemical properties of the synthesized Cu(I)adsorbent featuringπ-complexation and their correlations with the adsorption performance.Meanwhile,the first principal calculation software CP2K was used to develop an understanding of the adsorption mechanism,which can offer useful guidance for the adsorbent regeneration.The synthesized Cu(I)adsorbent,prepared by using copper citrate and citric acid on the ZSM-5(SiO_(2)/Al_(2)O_(3)=25)carrier,outperformed other adsorbents with varying formulations and carriers in adsorption capacities.Through optimization of the preparation and adsorption conditions for various adsorbents,the breakthrough adsorption capacity(Qb)for COS was further enhanced from 2.19 mg/g to 15.36 mg/g.The formed stableπ-complex bonds between COS and Cu(I),as confirmed by density func-tional theory calculations,were verified by the significant improvement in the adsorption capacity after regeneration at 600°C.The above advantages render the novel synthesized Cu(I)adsorbent a promising candidate featuring cost-effectiveness,high efficacy and good regenerability for desulfurization from a CO_(2)stream.
基金supported by the Scientific and Technological Innovation Project of Carbon Emission Peak and Carbon Neutrality of Jiangsu Province(No.BK20220001)the Big Data Computing Center of Southeast University.
文摘Sodium-based adsorbents(Na_(2)CO_(3)/γ-Al_(2)O_(3))exhibit significant potential for commercial utilization in CO_(2)capture.Nevertheless,the requirement for high desorption temperatures poses challenges in terms of the high-quality heat needed for desorption.This study integrated ZrO_(2)doping into a sodium-based adsorbent to enhance its CO_(2)capture performance and lower its desorption temperature.The research investigated the CO_(2)adsorption capacity,reaction rate,and desorption characteristics of the ZrO_(2)-doped Na_(2)CO_(3)/γ-Al_(2)O_(3)adsorbents in detail.Additionally,the catalytic mechanism of ZrO_(2)was elucidated through Density Functional Theory calculations.The results showed that ZrO_(2)doping increased the adsorption rate and capacity of the adsorbent and reduced the desorption energy consumption.Desorption reaction activation energy reduced to 44.8 kJ/mol.The adsorbent doped with 3wt.%ZrO_(2)demonstrated the highest adsorption capacity and rate under optimal conditions,with a reaction temperature of 45℃,an adsorption capacity of 1.66 mmol/g,and a carbon conversion rate of 80.2%.ZrO_(2)acted as a catalyst,enhancing CO_(2)and H_(2)O adsorption,and facilitated CO_(2)desorption in the sodium-based adsorbent by forming[ZrO(OH)]^(+)and OH^(−)through H_(2)O adsorption activation.The lower energy barrier(0.17 eV)for the dissociative adsorption pathway of H_(2)O molecules on the ZrO_(2)surface further supported the role of ZrO_(2)in enhancing the overall adsorption performance of the adsorbent in the carbon capture process.Ultimately,the ZrO_(2)-doped Na_(2)CO_(3)/γ-Al_(2)O_(3)adsorbent was identified as having low desorption energy consumption,high adsorption capacity,and rate,offering potential cost reductions in CO_(2)capture and representing a promising adsorbent for this application.
基金financial support from MICIU/AEI/10.13039/501100011033by the European Union,and grant MOE-T2EP10222-0007 from the Ministry of Education,Singapore。
文摘Density functional theory(DFT)has helped propel the advance of electrocatalysis in the past two decades.In view of its massive use,it is worth asking how reliable DFT is for the prediction of adsorption energies,which are paramount in computational electrocatalysis models.Here,we provide an experimental-computational approach to break down overall adsorption-energy errors into separate gas-phase and adsorbed-phase contributions.The method is evaluated using experimental data and various exchange-correlation functionals and materials for C-and O-containing species.Our main conclusion is that no functional is simultaneously accurate for adsorbates and molecules,as adsorbed-phase errors are visibly different from gas-phase errors.Importantly,total,gas-phase,and adsorbed-phase errors are correlated,revealing intrinsic DFT limitations and enabling the elaboration of swift correction routines.To illustrate the benefits of our approach,we deconvolute and correct all errors in CO_(2)electroreduction to CO and find an agreement with experiments close to chemical accuracy for numerous transition-metal electrodes and all scrutinized functionals.
基金Project supported by the Key Program of National High Technology Research and Development Program of China (863 Program) (2008AA062602)the Young and Middle-aged Academic and Technical Back-up Personnel Program of Yunnan Province (2007PY01-10)the Analysis and Measurement Foundation of Kunming University of Science & Technology
文摘A series of copper-based activated carbon (AC) adsorbents were prepared in order to investigate the effect of Zn, Ce addition on Cu-based AC adsorbent for phosphine (PH3) adsorption removal from yellow phosphorous tail gas. N2 adsorption isotherm and X-ray diffrac-tion (XRD) results suggested that the addition of Zn could increase the adsorbent ultramicropores, decrease the adsorbent supermicropores and the adsorbent average pore diameter. Therefore it enhanced the PH3 adsorption capacity. Appropriate amoun...
基金Project (50874045) supported by the National Natural Science Foundation of ChinaProjects (200902472, 20080431021) supported by the China Postdoctoral Science FoundationProject (10A044) supported by the Research Foundation of Education Bureau of Hunan Province of China
文摘Bulk Cu50Zr40Ti10 amorphous alloy composites reinforced with carbon nanotube （CNT） were successfully fabricated by hot pressing technique. Their density, thermal conductivity, and mechanical properties were systemically investigated. The density and the compression strength of the compacts both decrease with increasing CNT content. The thermal conductivity of the compacts decreases when the CNT content is less than 0.10% or exceeds 0.60% （mass fraction）, while increases when the CNT content is in the range of 0.1%-0.6%. The strain limit and the modulus of the compacts are obviously improved when the CNT content is less than 1.0% and then decrease significantly when the CNT content exceeds 1.00%. The optimum CNT addition is less than 0.20% at the comprehensive properties point of view.
基金Project(2008BAB35B04) supported by the National Key Technologies R&D Program of ChinaProject(2010QZZD003) supported by Central South University Advanced Research Program,China
文摘H2TiO3 was obtained from the acid-modified adsorbent precursor Li2TiO3,which was synthesized by a solid-phase reaction between TiO2 and Li2CO3.The extraction ratio of Li＋ from Li2TiO3 was 98.86%,almost with no Ti4＋ extracted.The effects of lithium titanium ratio,calcining temperature and time were investigated on the synthesis of Li2TiO3.Li2TiO3,H2TiO3 and the adsorbed Li＋ adsorbent were characterized by XRD and SEM.The lithium adsorption properties were investigated by the adsorption kinetics and adsorption isotherm.The results indicate that H2TiO3 has an excellent adsorptive capacity for Li＋.Two simplified kinetic models including the pseudo-first-order and pseudo-second-order equations were selected to follow the adsorption processes.The rate constants of adsorption for these kinetic models were calculated.The results show that the adsorption process can be described by the pseudo-second-order equation,and the process is proved to be a chemical adsorption.The adsorption process that H2TiO3 adsorbs Li＋ in LiCl solution well fits the Langmuir equation with monolayer adsorption.
