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
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
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
Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for ca...Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for catalytic reduction of CO_(2), Cu-based materials are highly advantageous owing to their widespread availability, cost-effectiveness, and environmental sustainability. Furthermore, Cu-based materials demonstrate interesting abilities in the adsorption and activation of carbon dioxide, allowing the formation of C_(2+) compounds through C–C coupling process. Herein, the basic principles of photocatalytic CO_(2) reduction reactions(PCO_(2)RR) and electrocatalytic CO_(2) reduction reaction(ECO_(2)RR) and the pathways for the generation C_(2+) products are introduced. This review categorizes Cu-based materials into different groups including Cu metal, Cu oxides, Cu alloys, and Cu SACs, Cu heterojunctions based on their catalytic applications. The relationship between the Cu surfaces and their efficiency in both PCO_(2)RR and ECO_(2)RR is emphasized. Through a review of recent studies on PCO_(2)RR and ECO_(2)RR using Cu-based catalysts, the focus is on understanding the underlying reasons for the enhanced selectivity toward C_(2+) products. Finally, the opportunities and challenges associated with Cu-based materials in the CO_(2) catalytic reduction applications are presented, along with research directions that can guide for the design of highly active and selective Cu-based materials for CO_(2) reduction processes in the future.展开更多
Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in re...Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in recent decades.Among the many products of CO_(2)RR(carbon monoxide,acids,aldehydes and alcohols,olefins,etc.),alcohols(methanol,ethanol,propanol,etc.)have a higher market value and energy density,but it is also more difficult to produce.Copper is known to be effective in catalyzing CO_(2) to high valueadded alcohols,but with poor selectivity.The progress of Cu-based catalysts for the selective generation of alcohols,including copper oxides,bimetals,single atoms and composites is reviewed.Meanwhile,to improve Cu-based catalyst activity and modulate product selectivity,the modulation strategies are straighten out,including morphological regulation,crystalline surface,oxidation state,as well as elemental doping and defect engineering.Based on the research progress of electrocatalytic CO_(2) reduction for alcohol production on Cu-based materials,the reaction pathways and the key intermediates of the electrocatalytic CO_(2)RR to methanol,ethanol and propanol are summarized.Finally,the problems of traditional electrocatalytic CO_(2)RR are introduced,and the future applications of machine learning and theoretical calculations are prospected.An in-depth discussion and a comprehensive review of the reaction mechanism,catalyst types and regulation strategies were carried out with a view to promoting the development of electrocatalytic CO_(2)RR to alcohols.展开更多
With the application of resins in various fields, numerous waste resins that are difficult to treat have been produced. The industrial wastewater containing Cr(Ⅵ) has severely polluted soil and groundwater environmen...With the application of resins in various fields, numerous waste resins that are difficult to treat have been produced. The industrial wastewater containing Cr(Ⅵ) has severely polluted soil and groundwater environments, thereby endangering human health. Therefore, in this paper, a novel functionalized mesoporous adsorbent PPR-Z was synthesized from waste amidoxime resin for adsorbing Cr(Ⅵ). The waste amidoxime resin was first modified with H3PO4 and ZnCl_(2), and subsequently, it was carbonized through slow thermal decomposition. The static adsorption of PPR-Z conforms to the pseudo-second-order kinetic model and Langmuir isotherm, indicating that the Cr(Ⅵ) adsorption by PPR-Z is mostly chemical adsorption and exhibits single-layer adsorption. The saturated adsorption capacity of the adsorbent for Cr(Ⅵ) could reach 255.86 mg/g. The adsorbent could effectively reduce Cr(Ⅵ) to Cr(Ⅲ) and decrease the toxicity of Cr(Ⅵ) during adsorption. PPR-Z exhibited Cr(Ⅵ) selectivity in electroplating wastewater. The main mechanisms involved in the Cr(Ⅵ) adsorption are the chemical reduction of Cr(Ⅵ) into Cr(Ⅲ) and electrostatic and coordination interactions. Preparation of PPR-Z not only solves the problem of waste resin treatment but also effectively controls Cr(Ⅵ) pollution and realizes the concept of “treating waste with waste”.展开更多
Electrocatalytic reduction of CO_(2)is crucial for environmental sustainability and renewable energy storage,with Cu-based catalysts excelling in producing high-value C_(2+)products.However,a comprehensive analysis of...Electrocatalytic reduction of CO_(2)is crucial for environmental sustainability and renewable energy storage,with Cu-based catalysts excelling in producing high-value C_(2+)products.However,a comprehensive analysis of how specific electrolyte influences Cu-based catalysts is lacking.This review addresses this gap by focusing on how electrolytes impact surface reconstruction and the CO_(2) reduction process on Cu-based electrocatalysts,identifying specific electrolyte compositions that enhance the density and stability of active sites,and providing insights into how different electrolyte environments modulate the selectivity and efficiency of C_(2+)product formation.The review begins by exploring how electrolytes induce favorable surface reconstruction in Cu-based catalysts,affecting surface roughness through dissolution-redeposition of Cu species and interactions with halogens and molecular additives.It also covers changes in crystalline facets of Cu and Cu_(2)O,and oxidation states,highlighting transitions from Cu^(0) to Cu^(δ+)and the stabilization of Cu^(+).The role of electrolytes in the C–C coupling process is examined,emphasizing their effects in modulating mass and charge transfer,CO_(2) adsorption,intermediate evolution,and product desorption.Subsequently,the mechanisms by non-aqueous electrolytes,including organic solvents,ionic liquids,and mixed electrolytes,affecting CO_(2) reduction are analyzed,highlighting the unique advantages and challenges of each type.The review concludes by addressing current challenges,proposing solutions,and research directions,such as optimizing electrolyte composition by integrating diverse cations and anions and employing advanced in-situ characterization techniques.These insights can significantly enhance CO_(2)reduction performance on Cu-based electrocatalysts,advancing efficient and sustainable green energy technologies.展开更多
The goal of this work is,first of all,to construct a mathematical model of the mass transfer process in porous adsorption layers,taking into account the fact that in most cases the adsorption process is carried out in...The goal of this work is,first of all,to construct a mathematical model of the mass transfer process in porous adsorption layers,taking into account the fact that in most cases the adsorption process is carried out in nonstationary technological modes,which requires a clear description of its various stages.The scientific contribution of the novel model is based on a probability approach allowing for deriving a differential equation that takes into account the diffusion migration of adsorbed particles.Solving this equation allows us to calculate the reduced degree of the adsorption surface coverage along the flow and,thereby,calculate the efficiency of the mass transfer process.The model also makes it possible to determine the slip coefficient,the internal diffusion coefficient and the degree of filling of the internal surface of the pores of the adsorbent layer,which corresponds to the completion of the initial stage of adsorption and the transition of the process to a stable mode.In this case,the problem is to calculate a non-isothermal turbulent boundary layer when flowing around the surface of an adsorbent.Next,the problem of identifying the main control parameters of the model has been solved.Based on such analysis and experimental studies to assess the influence of process control parameters,the patterns of adsorption purification and solution separation have been established and the design of a highly efficient adsorption apparatus with a fixed layer of porous adsorbent have been developed.展开更多
A novel amine-modified pillar[5]arene bonded porous silica adsorbent(DETA-P5S)was designed to be applied to dynamic CO_(2)adsorption and selective separation of CO_(2)over N_(2)and CH_(4)gases mixture.The results demo...A novel amine-modified pillar[5]arene bonded porous silica adsorbent(DETA-P5S)was designed to be applied to dynamic CO_(2)adsorption and selective separation of CO_(2)over N_(2)and CH_(4)gases mixture.The results demonstrated that reasonable introduction of DETA into the BE-P5 bonded silica support has sig nificantly increased the adsorption capacity of CO_(2).The DETA-P5S has the optimal adsorption capacity of 9.1 mmol/g with 5 vol%CO_(2)at 40℃.The main reason of this increased capacity could be attributed to the enhanced CO_(2)diffusion into porous adsorbent for its better dispersion in the pores of amine pillar[5]arene cavity and active site of DETA.Furthermore,the dynamic saturation adsorption capacitie of DETA-P5S were 7.11(0.37)and 6.18(0.44)mmol/g for CO_(2)/N_(2)and CO_(2)/CH_(4),respectively,both the ga mixtures showed high separation selectivity.Simultaneously,the DETA-P5S can maintain outstanding CO_(2)adsorption capacity after fifteen regeneration cycles.Consequently,the designed DETA-P5S could serve a a promising adsorbent for CO_(2)capture and storage.展开更多
Taking deep coal-rock gas in the Yulin and Daning-Jixian areas of the Ordos Basin,NW China,as the research object,full-diameter coal rock samples with different cleat/fracture development degrees from the Carboniferou...Taking deep coal-rock gas in the Yulin and Daning-Jixian areas of the Ordos Basin,NW China,as the research object,full-diameter coal rock samples with different cleat/fracture development degrees from the Carboniferous Benxi Formation were selected to conduct physical simulation and isotope monitoring experiments of the full-life-cycle depletion development of coal-rock gas.Based on the experimental results,a dual-medium carbon isotope fractionation(CIF)model coupling cleats/fractures and matrix pores was constructed,and an evaluation method for free gas production patterns was established to elucidate the carbon isotope fractionation mechanism and adsorbed/free gas production characteristics during deep coal-rock gas development.The results show that the deep coal-rock gas development process exhibits a three-stage carbon isotope fractionation pattern:“Stable(Ⅰ)→Decrease(Ⅱ)→Increase(Ⅲ)”.A rapid decline in boundary pressure in stageⅢleads to fluctuations in isotope value,characterized by a“rapid decrease followed by continued increase”,with free gas being produced first and long-term supply of adsorbed gas.The CIF model can effectively match measured gas pressure,cumulative gas production,and δ^(13)C_(1) value of produced gas.During the first two stages of isotope fractionation,free gas dominated cumulative production.During the mid-late stages of slow depletion production,the staged pressure control development method can effectively increase the gas recovery.The production of adsorbed gas is primarily controlled by the rock's adsorption capacity and the presence of secondary flow channels.Effectively enhancing the recovery of adsorbed gas during the late stage remains crucial for maintaining stable production and improving the ultimate recovery factor of deep coal-rock gas.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
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 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supported by the National Natural Science Foundation of China (22178149)Jiangsu Distinguished Professor Program+4 种基金Natural Science Foundation of Jiangsu Province for Outstanding Youth Scientists (BK20211599)Key R and D Project of Zhenjiang City (CQ2022001)Scientific Research Startup Foundation of Jiangsu University (Nos. 202096 and 22JDG020)Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment of Fuzhou University (SKLPEE-KF202310)the Opening Project of Structural Optimization and Application of Functional Molecules Key Laboratory of Sichuan Province (2023GNFZ-01)。
文摘Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for catalytic reduction of CO_(2), Cu-based materials are highly advantageous owing to their widespread availability, cost-effectiveness, and environmental sustainability. Furthermore, Cu-based materials demonstrate interesting abilities in the adsorption and activation of carbon dioxide, allowing the formation of C_(2+) compounds through C–C coupling process. Herein, the basic principles of photocatalytic CO_(2) reduction reactions(PCO_(2)RR) and electrocatalytic CO_(2) reduction reaction(ECO_(2)RR) and the pathways for the generation C_(2+) products are introduced. This review categorizes Cu-based materials into different groups including Cu metal, Cu oxides, Cu alloys, and Cu SACs, Cu heterojunctions based on their catalytic applications. The relationship between the Cu surfaces and their efficiency in both PCO_(2)RR and ECO_(2)RR is emphasized. Through a review of recent studies on PCO_(2)RR and ECO_(2)RR using Cu-based catalysts, the focus is on understanding the underlying reasons for the enhanced selectivity toward C_(2+) products. Finally, the opportunities and challenges associated with Cu-based materials in the CO_(2) catalytic reduction applications are presented, along with research directions that can guide for the design of highly active and selective Cu-based materials for CO_(2) reduction processes in the future.
基金supported by the Fundamental Research Funds for the Central Universities (FRF-EYIT-23-07)。
文摘Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in recent decades.Among the many products of CO_(2)RR(carbon monoxide,acids,aldehydes and alcohols,olefins,etc.),alcohols(methanol,ethanol,propanol,etc.)have a higher market value and energy density,but it is also more difficult to produce.Copper is known to be effective in catalyzing CO_(2) to high valueadded alcohols,but with poor selectivity.The progress of Cu-based catalysts for the selective generation of alcohols,including copper oxides,bimetals,single atoms and composites is reviewed.Meanwhile,to improve Cu-based catalyst activity and modulate product selectivity,the modulation strategies are straighten out,including morphological regulation,crystalline surface,oxidation state,as well as elemental doping and defect engineering.Based on the research progress of electrocatalytic CO_(2) reduction for alcohol production on Cu-based materials,the reaction pathways and the key intermediates of the electrocatalytic CO_(2)RR to methanol,ethanol and propanol are summarized.Finally,the problems of traditional electrocatalytic CO_(2)RR are introduced,and the future applications of machine learning and theoretical calculations are prospected.An in-depth discussion and a comprehensive review of the reaction mechanism,catalyst types and regulation strategies were carried out with a view to promoting the development of electrocatalytic CO_(2)RR to alcohols.
基金supported by the National Natural Science Foundation of China (No.52364022)the Natural Science Foundation of Guangxi Province,China (Nos.2023JJA160192 and 2021GXNSFAA220096)+1 种基金the Guangxi Science and Technology Major Project,China (No.AA23073018)the Guangxi Chongzuo Science and Technology Plan,China (No.2023ZY00503).
文摘With the application of resins in various fields, numerous waste resins that are difficult to treat have been produced. The industrial wastewater containing Cr(Ⅵ) has severely polluted soil and groundwater environments, thereby endangering human health. Therefore, in this paper, a novel functionalized mesoporous adsorbent PPR-Z was synthesized from waste amidoxime resin for adsorbing Cr(Ⅵ). The waste amidoxime resin was first modified with H3PO4 and ZnCl_(2), and subsequently, it was carbonized through slow thermal decomposition. The static adsorption of PPR-Z conforms to the pseudo-second-order kinetic model and Langmuir isotherm, indicating that the Cr(Ⅵ) adsorption by PPR-Z is mostly chemical adsorption and exhibits single-layer adsorption. The saturated adsorption capacity of the adsorbent for Cr(Ⅵ) could reach 255.86 mg/g. The adsorbent could effectively reduce Cr(Ⅵ) to Cr(Ⅲ) and decrease the toxicity of Cr(Ⅵ) during adsorption. PPR-Z exhibited Cr(Ⅵ) selectivity in electroplating wastewater. The main mechanisms involved in the Cr(Ⅵ) adsorption are the chemical reduction of Cr(Ⅵ) into Cr(Ⅲ) and electrostatic and coordination interactions. Preparation of PPR-Z not only solves the problem of waste resin treatment but also effectively controls Cr(Ⅵ) pollution and realizes the concept of “treating waste with waste”.
基金supported by the Hubei Provincial Natural Science Foundation of China (2023AFB0049)the Scientific Research Fund Project of Wuhan Institute of Technology (No.K2024006)the Graduate Education Innovation Fund of Wuhan Institute of Technology (No. CX2023091)。
文摘Electrocatalytic reduction of CO_(2)is crucial for environmental sustainability and renewable energy storage,with Cu-based catalysts excelling in producing high-value C_(2+)products.However,a comprehensive analysis of how specific electrolyte influences Cu-based catalysts is lacking.This review addresses this gap by focusing on how electrolytes impact surface reconstruction and the CO_(2) reduction process on Cu-based electrocatalysts,identifying specific electrolyte compositions that enhance the density and stability of active sites,and providing insights into how different electrolyte environments modulate the selectivity and efficiency of C_(2+)product formation.The review begins by exploring how electrolytes induce favorable surface reconstruction in Cu-based catalysts,affecting surface roughness through dissolution-redeposition of Cu species and interactions with halogens and molecular additives.It also covers changes in crystalline facets of Cu and Cu_(2)O,and oxidation states,highlighting transitions from Cu^(0) to Cu^(δ+)and the stabilization of Cu^(+).The role of electrolytes in the C–C coupling process is examined,emphasizing their effects in modulating mass and charge transfer,CO_(2) adsorption,intermediate evolution,and product desorption.Subsequently,the mechanisms by non-aqueous electrolytes,including organic solvents,ionic liquids,and mixed electrolytes,affecting CO_(2) reduction are analyzed,highlighting the unique advantages and challenges of each type.The review concludes by addressing current challenges,proposing solutions,and research directions,such as optimizing electrolyte composition by integrating diverse cations and anions and employing advanced in-situ characterization techniques.These insights can significantly enhance CO_(2)reduction performance on Cu-based electrocatalysts,advancing efficient and sustainable green energy technologies.
基金funded by the Ministry of Science and Higher Education of the Republic of Kazakhstan(grant number AP19678142)。
文摘The goal of this work is,first of all,to construct a mathematical model of the mass transfer process in porous adsorption layers,taking into account the fact that in most cases the adsorption process is carried out in nonstationary technological modes,which requires a clear description of its various stages.The scientific contribution of the novel model is based on a probability approach allowing for deriving a differential equation that takes into account the diffusion migration of adsorbed particles.Solving this equation allows us to calculate the reduced degree of the adsorption surface coverage along the flow and,thereby,calculate the efficiency of the mass transfer process.The model also makes it possible to determine the slip coefficient,the internal diffusion coefficient and the degree of filling of the internal surface of the pores of the adsorbent layer,which corresponds to the completion of the initial stage of adsorption and the transition of the process to a stable mode.In this case,the problem is to calculate a non-isothermal turbulent boundary layer when flowing around the surface of an adsorbent.Next,the problem of identifying the main control parameters of the model has been solved.Based on such analysis and experimental studies to assess the influence of process control parameters,the patterns of adsorption purification and solution separation have been established and the design of a highly efficient adsorption apparatus with a fixed layer of porous adsorbent have been developed.
基金financial supports from National Natural Science Foundation of China(No.22204169)Gansu Natural Science Foundation(Nos.23JRRA619,21JR7RA076)Scientific and Technological Program of Chengguan District,Lanzhou(No.2023JSCX0037)。
文摘A novel amine-modified pillar[5]arene bonded porous silica adsorbent(DETA-P5S)was designed to be applied to dynamic CO_(2)adsorption and selective separation of CO_(2)over N_(2)and CH_(4)gases mixture.The results demonstrated that reasonable introduction of DETA into the BE-P5 bonded silica support has sig nificantly increased the adsorption capacity of CO_(2).The DETA-P5S has the optimal adsorption capacity of 9.1 mmol/g with 5 vol%CO_(2)at 40℃.The main reason of this increased capacity could be attributed to the enhanced CO_(2)diffusion into porous adsorbent for its better dispersion in the pores of amine pillar[5]arene cavity and active site of DETA.Furthermore,the dynamic saturation adsorption capacitie of DETA-P5S were 7.11(0.37)and 6.18(0.44)mmol/g for CO_(2)/N_(2)and CO_(2)/CH_(4),respectively,both the ga mixtures showed high separation selectivity.Simultaneously,the DETA-P5S can maintain outstanding CO_(2)adsorption capacity after fifteen regeneration cycles.Consequently,the designed DETA-P5S could serve a a promising adsorbent for CO_(2)capture and storage.
基金Youth Fund of National Natural Science Foundation of China(42302170)CNPC Scientific and Technological Innovation Fund(2022DQ02-0104)RIPED Open Project Fund(2024-KFKT-31).
文摘Taking deep coal-rock gas in the Yulin and Daning-Jixian areas of the Ordos Basin,NW China,as the research object,full-diameter coal rock samples with different cleat/fracture development degrees from the Carboniferous Benxi Formation were selected to conduct physical simulation and isotope monitoring experiments of the full-life-cycle depletion development of coal-rock gas.Based on the experimental results,a dual-medium carbon isotope fractionation(CIF)model coupling cleats/fractures and matrix pores was constructed,and an evaluation method for free gas production patterns was established to elucidate the carbon isotope fractionation mechanism and adsorbed/free gas production characteristics during deep coal-rock gas development.The results show that the deep coal-rock gas development process exhibits a three-stage carbon isotope fractionation pattern:“Stable(Ⅰ)→Decrease(Ⅱ)→Increase(Ⅲ)”.A rapid decline in boundary pressure in stageⅢleads to fluctuations in isotope value,characterized by a“rapid decrease followed by continued increase”,with free gas being produced first and long-term supply of adsorbed gas.The CIF model can effectively match measured gas pressure,cumulative gas production,and δ^(13)C_(1) value of produced gas.During the first two stages of isotope fractionation,free gas dominated cumulative production.During the mid-late stages of slow depletion production,the staged pressure control development method can effectively increase the gas recovery.The production of adsorbed gas is primarily controlled by the rock's adsorption capacity and the presence of secondary flow channels.Effectively enhancing the recovery of adsorbed gas during the late stage remains crucial for maintaining stable production and improving the ultimate recovery factor of deep coal-rock gas.
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.
