Graphene-based materials possess significant potential for the treatment of dye wastewater due to their exceptional adsorption properties toward stubborn pollutants.However,their utilization is hindered by high prepar...Graphene-based materials possess significant potential for the treatment of dye wastewater due to their exceptional adsorption properties toward stubborn pollutants.However,their utilization is hindered by high preparation costs,low yields,environmental pollution during synthesis,and challenges in regenerating the adsorbent.This study proposes a novel approach to address these limitations by developing nitrogen-doped three-dimensional(3D)polyvinyl alcohol(PVA)crosslinked graphene sponges(N-PGA)using a cross-linking method with ammonium carbonate.This method offers a relatively mild,environmentally friendly approach.Ammonium carbonate serves as both a reducing and modifying agent,facilitating the formation of the intrinsic structure of N-PGA and acting as a nitrogen source.Meanwhile,PVA is utilized as the cross-linking agent.The results demonstrate that N-PGA exhibits a favorable internal 3D hierarchical porous structure and possesses robust mechanical properties.The measured specific surface area(BET)of N-PGA was as high as406.538 m^(2)·g^(-1),which was favorable for its efficient adsorption of Congo red(CR)dye molecules.At an initial concentration of 50 mg·L^(-1),N-PGA achieved an impressive removal rate of 89.6%and an adsorption capacity of 112 mg·g^(-1)for CR dye.Furthermore,it retained 79%of its initial adsorption capacity after 10 cycles,demonstrating excellent regeneration performance.In summary,the synthesized N-PGA displays remarkable efficacy in the adsorption of CR dye in wastewater,opening up new possibilities for utilizing 3D porous graphene nanomaterials as efficient adsorbents in wastewater treatment.展开更多
The adsorptive separation of C_(2)H_(4)and C_(2)H_(6),as an alternative to distillation units consuming high energy,is a promising yet challenging research.The great similarity in the molecular size of C_(2)H_(4)and C...The adsorptive separation of C_(2)H_(4)and C_(2)H_(6),as an alternative to distillation units consuming high energy,is a promising yet challenging research.The great similarity in the molecular size of C_(2)H_(4)and C_(2)H_(6)brings challenges to the regulation of adsorbents to realize efficient dynamic separation.Herein,we reported the enhancement of the kinetic separation of C_(2)H_(4)/C_(2)H_(6)by controlling the crystal size of ZnAtzPO_(4)(Atz=3-amino-1,2,4-triazole)to amplify the diffusion difference of C_(2)H_(4)and C_(2)H_(6).Through adjusting the synthesis temperature,reactant concentration,and ligands/metal ions molar ratio,ZnAtzPO4 crystals with different sizes were obtained.Both single-component kinetic adsorption tests and binary-component dynamic breakthrough experiments confirmed the enhancement of the dynamic separation of C_(2)H_(4)/C_(2)H_(6)with the increase in the crystal size of ZnAtzPO_(4).The separation selectivity of C_(2)H_(4)/C_(2)H_(6)increased from 1.3 to 98.5 with the increase in the crystal size of ZnAtzPO_(4).This work demonstrated the role of morphology and size control of adsorbent crystals in the improvement of the C_(2)H_(4)/C_(2)H_(6)kinetic separation performance.展开更多
A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structur...A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structure and the defective sites of h-BNNS not only are beneficial to the stabilization of Pt NPs but also favor the adsorption of aromatic sulfides.By employing Pt/h-BNNS with a Pt loading amount of 1.19 wt%as the active adsorbent and air as an oxidant,a 98.0%sulfur removal over dibenzothiophene(DBT)is achieved along with a total conversion of the DBT to the corresponding sulfones(DBTO_(2)).Detailed experiments show that the excellent desulfurization activity originates from the few-layered structure of h-BNNS and the high catalytic activity of Pt NPs.In addition,the OPADS system with Pt/h-BNNS as the active adsorbent shows remarkable stability in desulfurization performance with the existence of different interferents such as olefin,and aromatic hydrocarbons.Besides,the Pt/h-BNNS can be recycled 12 times without a significant decrease in desulfurization performance.Also,a process flow diagram is proposed for deep desulfurization of fuel oil and recovery of high value-added products,which would promote the industrial application of such OPADS strategy.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
Two major problems facing agriculture at present are soil pollution and the disposal of solid wastes generated during plant growth. The method of preparing biochar from solid wastes produced by plants is a means of ma...Two major problems facing agriculture at present are soil pollution and the disposal of solid wastes generated during plant growth. The method of preparing biochar from solid wastes produced by plants is a means of maximizing the use of resources to combat the problem of soil pollution. In this study, we did not choose straw in the traditional sense but the waste branches from grape pruning, which has higher lignin cellulose, as the raw material. The biochar derived from grape branches pyrolyzed at 300˚C for two hours was utilized as a raw material to prepare modified biochar with varying concentrations of phosphoric acid. The adsorption performance and mechanism of Cd<sup>2 </sup> were explored through experiments involving different concentrations, addition amounts, reaction times, kinetic analyses, and isothermal adsorption tests. The findings indicated that the optimal adsorption of Cd<sup>2 </sup> occurred with a 20% phosphoric acid concentration, achieving the highest adsorption rate of 84.62%. At a dosage of 10 g/L, the maximum adsorption capacity reached 7.02 mg/g. The adsorption kinetics and isothermal adsorption of Cd<sup>2 </sup> on biochar modified with 0.2% phosphoric acid (0.2 PB) closely followed the pseudo-first-order kinetics model (R<sup>2</sup> > 0.98) and the Freundlich model (R<sup>2</sup> > 0.97), respectively. This suggests that the adsorption process involves both physical and chemical mechanisms. SEM and FTIR analyses revealed that phosphoric acid modification primarily increased the biochar’s specific surface area and enhanced certain original functional groups. The adsorption process predominantly involved rapid ion diffusion and chemical adsorption, as confirmed by kinetic analysis and isothermal adsorption model analysis. In summary, the adsorption efficiency of 0.2 PB significantly improved, showing potential and feasibility for heavy metal remediation in soil. This supports the environmentally friendly concept of “treating waste with waste”.展开更多
Yala swamp wetland is the largest fresh water wetland ecosystem in Kenya supporting a broad biodiversity. It comprises of River Yala, the Yala swamp, Lakes Kanyaboli, Namboyo and Sare, and a portion of Lake Victoria n...Yala swamp wetland is the largest fresh water wetland ecosystem in Kenya supporting a broad biodiversity. It comprises of River Yala, the Yala swamp, Lakes Kanyaboli, Namboyo and Sare, and a portion of Lake Victoria neighboring the swamp. Approximately 2300 ha of land have been reclaimed and has been used for large-scale agriculture resulting in mass destruction of papyrus to create room for framing. Papyrus are known to be important in phytoremediation but despite this role information is limited, lacks supportive evidence and the empirical aspect on the levels of these pollutants in relation to the papyrus biomass is limited. The study is aimed at determining the effects of Cyperus papyrus on the water and sediment quality in Yala Swamp wetland. Six sampling sites were purposefully selected to monitor the variations of the physicochemical parameters (temperature, dissolved oxygen: DO, pH, biological oxygen demand: BOD, total suspended solids: TSS, turbidity, electrical conductivity: EC and total dissolved solids: TSS) and the levels selected nutrients (phosphorus and nitrates) in water and sediments as River Yala flows through Dominion Farms, Lake Sare which surrounded by Cyperus papyrus and finally into Lake Victoria. The samples were collected in triplicates during the wet and dry seasons (May and September 2015 respectively). The physicochemical parameters were measured in situ using a Hydrolab muiltimeter while the nutrients were analyzed using UV/Vis spectroscopy. Statistical analysis was done using SAS V9.0 software. The mean temperature was 26.19˚C ± 0.71˚C, DO: 3.72 ± 1.02 Mg/l, BOD: 3.9 ± 0.32 Mg/l, pH: 7.52 ± 0.17, TDS: 109 ± 86.33, EC: 173.26 ± 13.8 μS/cm, TSS: 12.42 ± 18.51 Mg/l and Turbidity: 12.29 ± 10.03 NTU. The values varied significantly at P 0.05 among all the sites. The results show that papyrus is useful in maintaining the required levels of physicochemical parameters. The study will assist in conservation of the papyrus to help phytoremediate pollutants from Dominion farms and the adjacent farms in order to have ecologically sound wetland.展开更多
In this study, new nano spherical graphene modified with LDH(Layered Double Hydroxide) was prepared and used to remove As(Ⅲ) ion from aqueous solutions. At first, graphene oxide was synthesized from graphite using a ...In this study, new nano spherical graphene modified with LDH(Layered Double Hydroxide) was prepared and used to remove As(Ⅲ) ion from aqueous solutions. At first, graphene oxide was synthesized from graphite using a well-known Hammer method. The obtained graphene oxide solution was sprayed in octanol solution under different temperatures and sprayed speed as influenced variables. The structure and physical characterization of synthesized spherical graphene oxide were determined by various techniques,including FT-IR, N_(2) adsorption–desorption, SEM, TEM, and EDX. In the next step, the hydrothermal method was applied to deposition LDH on the spherical graphene oxide. The synthesized spherical graphene modified by LDH was used to remove As(Ⅲ) as a toxic heavy metal ion. The effect of influenced variables including p H, contact time, amount of sorbent, and type eluent studied and the optimum values were as 8, 30, 50, and HCl(0.5 mol·L^(-1)), respectively. After optimization, the studied sorbent was shown a high adsorption capacity(149.3 mg·g^(-1)). The adsorption mechanism and kinetic models exhibited good agreement with the Langmuir isotherm and pseudo-second-order trends, respectively. Besides, the synthesized product was tested for seven times without significant loss in its sorption efficiency.展开更多
Zearalenone is a mycotoxin produced by Fusarium species.It frequently contaminates cereals used for foods or animal feeds,especially deposited in crude corn oil.Certain amounts of zearalenone can be removed during ref...Zearalenone is a mycotoxin produced by Fusarium species.It frequently contaminates cereals used for foods or animal feeds,especially deposited in crude corn oil.Certain amounts of zearalenone can be removed during refining processes.In this study,we studied the influence of activated carbon and six industial absorbents(zeolite,diatomite,attapulgite,perlite,montmorillonite and activated clay)on the elimination of zearalenone during bleaching process of corn oil and explored the absorption mechanism of activated carbon.Results showed that activated carbon had an excellent adsorption capacity of zearalenone compared with the other six industrial adsorbents.For activated carbon,a high removal rate of zearalenone(exceeding 83%)from heavily zearalenone-polluted corn oil was achieved and the removal rate of zearalenone was kept above 60%after five regeneration cycles.The research on the adsorption mechanism of activated carbon showed that Freundlich adsorption isotherm model and pseudo-second-order kinetic model could well described the adsorption process.The thermodynamic study demonstrated that adsorption process was spontaneous and exothermic.Fourier transform infrared spectroscopy and Raman spectroscopy further revealed that activated carbon was effectively combined with zearalenone viaπ-πinteraction.Thus,activated carbon is an efficient and suitable adsorbent to control the levels of zearalenone during bleaching process of corn oil.This study not only proposed a systematic research scheme for the mechanism study of activated carbon for the elimination of zearalenone in corn oil,but also provided the scientific basis for developing effective methods to eliminate zearalenone in refined vegetable oils.展开更多
Synthesis of mixed matrix membranes(MMM)using carbon nanotubes(CNTs)has shown great prospects for achieving excellent selective separation because of its special structure.Nevertheless,the preparation of highly select...Synthesis of mixed matrix membranes(MMM)using carbon nanotubes(CNTs)has shown great prospects for achieving excellent selective separation because of its special structure.Nevertheless,the preparation of highly selective MMM faces challenges,which is attributed to the obstacles encountered by CNTs dispersion in polymer matrix and elimination of interface defects.A novel CNT-based composite decorated with metal–organic framework(MOF)was synthesized and applied to the preparation of MMM.MOF was post modified,and then carboxyl groups were inserted on the outer surface of CNTs.The synthetic MMM(Cu-MOF-en@MWCNT)not only has selective adsorption on dyes,but also has selective photodegradation on dyes.The method of using CNTs to wrap the outside of MOF has great potential in dye separation.The performance of MMM was further improved by decorating MOF on the filler to improve the selectivity to the designated dye.展开更多
Carbon is a normally used adsorbent for removal of heavy metal ion in aqueous solutions,but the efficient adsorbent needs intensive modification by heteroatom doped or supported noble metals that cause severe pollutio...Carbon is a normally used adsorbent for removal of heavy metal ion in aqueous solutions,but the efficient adsorbent needs intensive modification by heteroatom doped or supported noble metals that cause severe pollution and easy leaching of active components during use.In this paper,the role of intrinsic defects on Hg^(2+)adsorption for carbon adsorbent was investigated.The maximum adsorbing capacity of defectrich carbon has been improved up to 433 mg·g^(-1)which is comparable to most of the modified carbon adsorbents via supported metal chloride or noble metal components.The basicity is increased with the content of defective sites and the strong chemical bonding can be formed via electron transformation between the defect sites with adsorbed Hg^(2+).The present study gives a direction to explore cheap and easily scale-up high-performance mercury adsorbents by simply tuning the intrinsic defective structure of carbon without the necessity to support metal or other organic compounds.展开更多
Water pollution regarding dyes and heavy metal ions is crucial facing the world.How to effectively separate these contaminants from water has been a key issue.Graphene oxide(GO)promises the greenwater world as a long-...Water pollution regarding dyes and heavy metal ions is crucial facing the world.How to effectively separate these contaminants from water has been a key issue.Graphene oxide(GO)promises the greenwater world as a long-lasting spotlight adsorbent material and therefore,harnessing GO has been the research hotspot for over a decade.The state of GO as well as its surface functional groups plays an important role in adsorption.And the way of preparation and structural modification matters to the performance of GO.In this review,the significance of the state of existence of stock GO and surface functional groups is explored in terms of preparation,structural modification,and adsorption.Besides,various adsorbates for GO adsorption are also involved,the discussion of which is rarely established elsewhere.展开更多
Porous polymer(pyrrolopyrrole)was successfully prepared via domino-ring-formation reaction.The chemical-physical properties of cyanided covalent triazine frameworks(CTF-CN)were characteriazed by fourier transform infr...Porous polymer(pyrrolopyrrole)was successfully prepared via domino-ring-formation reaction.The chemical-physical properties of cyanided covalent triazine frameworks(CTF-CN)were characteriazed by fourier transform infrared spectra(FT-IR),scanning electron microscopy(SEM),nuclear magnetic resonance(NMR),specific surface area analyzer(BET)and thermogravimetric analysis(TGA),respectively.The experimental results of adsorption of chloranil(TCBQ)in aqueous solution indicated that CTF-CN exhibited distinctive adsorption capacity toward TCBQ owing to its large specific surface area.Specifically,the adsorption equilibrium of as-prepared polymer was executed within 5 h and the calculated adsorption capacity was 499.76 mg/g.Furthermore,the adsorption kinetics could be well defined with the linear pseudo-second-order model,which implies that the chemical interaction are relative important in the course of TCBQ removal.Finally,the current studies verify that CTF-CN has unique rigid and nano-porous framework structure,which can be employed for the treatment of a series of harmful aromatic substances.展开更多
Because of the influence of hydrocarbons,especially adsorbed hydrocarbons,on the detection of cracked hydrocarbon(S2)and total organic carbon(TOC),the hydrogen index(HI)-based hydrocarbon generation model deviates fro...Because of the influence of hydrocarbons,especially adsorbed hydrocarbons,on the detection of cracked hydrocarbon(S2)and total organic carbon(TOC),the hydrogen index(HI)-based hydrocarbon generation model deviates from actual practice.In this study,the shale in the first member of the Qingshankou Formation in the central depression of the Songliao Basin,where in northeastern China,was taken as the research object and a correction method for S2 and TOC was established.By correcting the experimental results of different maturity samples,the actual hydrocarbon generation model has been revealed,the differences before and after correction compared,and the evolutionary characteristics of the adsorbed hydrocarbon content were clarified.The results show that the organic matter enters the hydrocarbon generation threshold at R_(o)-0.5% and reaches the hydrocarbon generation peak at R_(o)-1.0% and that the hydrocarbon generation process ends at R_(o)-1.3%.The hydrocarbon generation model established based on the measured values has a‘lag effect’compared to actual values,and this extends the hydrocarbon generation window of organic matter and delays the hydrocarbon generation peak.With the increase of maturity,adsorbed hydrocarbon content shows the characteristics of‘first increasing,then stabilizing,and then decreasing’,and reache s the most abundant stage at Roof 0.9%-1.3%.展开更多
To better understand the role of the-NH_(2)group in adsorption process of phenolic wastewaters,NH_(2)-functionalized MIL-53(Al)composites with activated carbon(NH_(2)-M(Al)@(B)AC)were prepared.The results showed that ...To better understand the role of the-NH_(2)group in adsorption process of phenolic wastewaters,NH_(2)-functionalized MIL-53(Al)composites with activated carbon(NH_(2)-M(Al)@(B)AC)were prepared.The results showed that the-NH_(2)group could increase the mesopore volume for composites,which promotes mass transfer and full utilization of active sites,because hierarchical mesopore structure makes the adsorbent easier to enter the internal adsorption sites.Furthermore,the introduction of the-NH_(2)group can improve the adsorption capacity,decrease the activation energy,and enhance the interaction between the adsorbent and p-nitrophenol,demonstrating that the-NH_(2)group plays a crucial role in the adsorption of p-nitrophenol.The density functional theory calculation results show that the H-bond interaction between the-NH_(2)group in the adsorbent and the-NO_(2)in the p-nitrophenol(adsorption energy of -35.5 kJ·mol^(-1)),and base-acid interaction between the primary-NH_(2)group in the adsorbent and the acidic-OH group in the p-nitrophenol(adsorption energy of -27.3 kJ·mol^(-1))are predominant mechanisms for adsorption in terms of the NH_(2)-functionalized adsorbent.Both NH_(2)-functionalized M(Al)@AC and M(Al)@BAC composites exhibited higher p-nitrophenol adsorption capacity than corresponding nonfunctionalized composites.Among the composites,the NH_(2)-M(Al)@BAC had the highest p-nitrophenol adsorption capacity of 474 mg·g^(-1).展开更多
Carbon monoxide(CO)is an impurity gas that can poison the precious metal catalysts of hydrogen fuel cells,so it is necessary to separate CO from hydrogen.In this paper,an isovolumetric impregnation method was develope...Carbon monoxide(CO)is an impurity gas that can poison the precious metal catalysts of hydrogen fuel cells,so it is necessary to separate CO from hydrogen.In this paper,an isovolumetric impregnation method was developed to prepare Cu(I)-supported activated carbon(AC),which is simple and easy to industrialize.The prepared cuprous chloride CuCl/AC adsorbent displayed a high CO adsorption capacity of 82.1 cm^(3)/g and a high CO/H_(2) separation factor of 20 at 20 bar and 298 K.This material can adsorb and remove CO from CO/H_(2) mixed gas(5μL/L CO-balanced H_(2))to less than 0.2μL/L under dynamic flow conditions,and showed excellent regeneration performance.The results show that CuCl/AC is an effective adsorbent for separating trace CO in high-purity hydrogen.展开更多
A quantitative evaluation model that integrates kerogen adsorption and clay pore adsorption of shale oil was proposed,and the evaluation charts of adsorption-swelling capacity of kerogen(Mk)and adsorbed oil capacity o...A quantitative evaluation model that integrates kerogen adsorption and clay pore adsorption of shale oil was proposed,and the evaluation charts of adsorption-swelling capacity of kerogen(Mk)and adsorbed oil capacity of clay minerals(Mc)were established,taking the 1st member of Cretaceous Qingshankou Formation in the northern Songliao Basin as an example.The model and charts were derived from swelling oil experiments performed on naturally evolved kerogens and adsorbed oil experiments on clays(separated from shale core samples).They were constructed on the basis of clarifying the control law of kerogen maturity evolution on its adsorption-swelling capacity,and considering the effect of both the clay pore surface area that occupied by adsorbed oil and formation temperature.The results are obtained in four aspects:(1)For the Qing 1 Member shale,with the increase of maturity,Mk decreases.Given Ro of 0.83%–1.65%,Mk is about 50–250 mg/g.(2)The clay in shale adsorbs asphaltene.Mc is 0.63 mg/m^(2),and about 15%of the clay pore surface is occupied by adsorbed oil.(3)In the low to medium maturity stages,the shale oil adsorption is controlled by organic matter.When Ro>1.3%,the shale oil adsorption capacity is contributed by clay pores.(4)The oil adsorption capacity evaluated on the surface at room temperature is 8%–22%(avg.15%)higher than that is held in the formations.The proposed evaluation model reveals the occurrence mechanisms of shale oils with different maturities,and provides a new insight for estimating the reserves of shale oil under formation temperature conditions.展开更多
Based on the drilling, logging, experimental and testing data of Well PD1, a shallow normal-pressure shale gas well in the Laochangping anticline in southeastern Sichuan Basin, the shallow shale gas reservoirs of the ...Based on the drilling, logging, experimental and testing data of Well PD1, a shallow normal-pressure shale gas well in the Laochangping anticline in southeastern Sichuan Basin, the shallow shale gas reservoirs of the Ordovician Wufeng Formation to Silurian Longmaxi Formation (Wufeng-Longmaxi) were investigated in terms of geological characteristics, occurrence mechanism, and adsorption-desorption characteristics, to reveal the enrichment laws and high-yield mechanism of shallow normal-pressure shale gas in complex structure areas. First, the shallow shale gas reservoirs are similar to the medium-deep shale gas reservoirs in static indicators such as high-quality shale thickness, geochemistry, physical properties and mineral composition, but the former is geologically characterized by low formation pressure coefficient, low gas content, high proportion of adsorbed gas, low in-situ stress, and big difference between principal stresses. Second, shallow shales in the complex structure areas have the gas occurrence characteristics including low total gas content (1.1-4.8 m3/t), high adsorbed gas content (2.5-2.8 m3/t), low sensitive desorption pressure (1.7-2.5 MPa), and good self-sealing. Third, the adsorbed gas enrichment of shales is mainly controlled by organic matter abundance, formation temperature and formation pressure: the higher the organic matter abundance and formation pressure, the lower the formation temperature and the higher the adsorption capacity, which is more beneficial for the adsorbed gas occurrence. Fourth, the shallow normal-pressure shale gas corresponds to low sensitive desorption pressure. The adsorbed gas can be rapidly desorbed and recovered when the flowing pressure is reduced below the sensitive desorption pressure. Fifth, the exploration breakthrough of Well PD1 demonstrates that the shallow complex structure areas with adsorbed gas in dominance can form large-scale shale reservoirs, and confirms the good exploration potential of shallow normal-pressure shale gas in the margin of the Sichuan Basin.展开更多
CO impurity-induced catalyst deactivation has long been one of the biggest challenges in proton-exchange membrane fuel cells,with the poisoning phenomenon mainly attributed to the overly strong adsorption on the catal...CO impurity-induced catalyst deactivation has long been one of the biggest challenges in proton-exchange membrane fuel cells,with the poisoning phenomenon mainly attributed to the overly strong adsorption on the catalytic site.Here,we present a mechanistic study that overturns this understanding by using Rh-based single-atom catalysis centers as model catalysts.We precisely modulated the chelation structure of the Rh catalyst by coordinating Rh with C or N atoms,and probed the reaction mechanism by surface-enhanced Raman spectroscopy.Direct spectroscopic evidence for intermediates indicates that the reactivity of adsorbed OH^(*),rather than the adsorption strength of CO^(*),dictates the CO electrocatalytic oxidation behavior.The RhN_(4)sites,which adsorb the OH^(*)intermediate more weakly than RhC4 sites,showed prominent CO oxidation activity that not only far exceeded the traditional Pt/C but also the RhC4 sites with similar CO adsorption strength.From this study,it is clear that a paradigm shift in future research should be considered to rationally design high-performance CO electro-oxidation reaction catalysts by sufficiently considering the water-related reaction intermediate during catalysis.展开更多
Water electrolysis,a process for producing green hydrogen from renewable energy,plays a crucial role in the transition toward a sustainable energy landscape and the realization of the hydrogen economy.Oxygen evolution...Water electrolysis,a process for producing green hydrogen from renewable energy,plays a crucial role in the transition toward a sustainable energy landscape and the realization of the hydrogen economy.Oxygen evolution reaction(OER)is a critical step in water electrolysis and is often limited by its slow kinetics.Two main mechanisms,namely the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM),are commonly considered in the context of OER.However,designing efficient catalysts based on either the AEM or the LOM remains a topic of debate,and there is no consensus on whether activity and stability are directly related to a certain mechanism.Considering the above,we discuss the characteristics,advantages,and disadvantages of AEM and LOM.Additionally,we provide insights on leveraging the LOM to develop highly active and stable OER catalysts in future.For instance,it is essential to accurately differentiate between reversible and irreversible lattice oxygen redox reactions to elucidate the LOM.Furthermore,we discuss strategies for effectively activating lattice oxygen to achieve controllable steady-state exchange between lattice oxygen and an electrolyte(OH^(-)or H_(2)O).Additionally,we discuss the use of in situ characterization techniques and theoretical calculations as promising avenues for further elucidating the LOM.展开更多
To meet the emission standard of nitrogen oxides(NOx)in the flue gas of batch furnaces through dry adsorption,a calcium-silica inorganic adsorbent was prepared with limestone and quartz as raw materials.Sample Cu-BTC ...To meet the emission standard of nitrogen oxides(NOx)in the flue gas of batch furnaces through dry adsorption,a calcium-silica inorganic adsorbent was prepared with limestone and quartz as raw materials.Sample Cu-BTC 1#was obtained by solvothermal synthesis,drying and purification in vacuum at 120℃using trimesic acid(H3BTC)and copper nitrate trihydrate(Cu(NO_(3))2·3H_(2)O)as raw materials;likewise,sample Cu-BTC 3#was obtained at 200℃.Sample Cu-BTC 2#was obtained by hydrothermal synthesis,drying and purification in air(metal-organic frameworks,1,3,5-benzene tricarboxylic acid copper).The two types of materials were tested in terms of the NO_(2) adsorption,and then the specific surface area,pore volume,NO_(2) adsorption performance,phase composition,microstructure and thermal stability of the adsorbent materials were exploredvia N_(2) physical adsorption-desorption,SEM,XRD and TG characterization.The results show that:(1)the Cu-BTC samples have higher adsorption capacity than the calcium-silica adsorbent,in which sample Cu-BTC 3#has the largest specific surface area and pore volume,thus adsorption capacity for NO_(2);(2)the calcium-silica adsorbent has better thermal stability and lower total mass loss during the entire process than the Cu-BTC samples;sample Cu-BTC 2#has the best thermal stability among the three Cu-BTC samples,and the metal Cu active sites of the Cu-BTC samples can be exposed at least above 150℃.展开更多
基金supported by the National Natural Science Foundation of China(51671052,51750110513,52250610222)the Fundamental Research Funds for the Central Universities(N182502042)the Liao Ning Revitilization Talents Program(XLYC1902105)。
文摘Graphene-based materials possess significant potential for the treatment of dye wastewater due to their exceptional adsorption properties toward stubborn pollutants.However,their utilization is hindered by high preparation costs,low yields,environmental pollution during synthesis,and challenges in regenerating the adsorbent.This study proposes a novel approach to address these limitations by developing nitrogen-doped three-dimensional(3D)polyvinyl alcohol(PVA)crosslinked graphene sponges(N-PGA)using a cross-linking method with ammonium carbonate.This method offers a relatively mild,environmentally friendly approach.Ammonium carbonate serves as both a reducing and modifying agent,facilitating the formation of the intrinsic structure of N-PGA and acting as a nitrogen source.Meanwhile,PVA is utilized as the cross-linking agent.The results demonstrate that N-PGA exhibits a favorable internal 3D hierarchical porous structure and possesses robust mechanical properties.The measured specific surface area(BET)of N-PGA was as high as406.538 m^(2)·g^(-1),which was favorable for its efficient adsorption of Congo red(CR)dye molecules.At an initial concentration of 50 mg·L^(-1),N-PGA achieved an impressive removal rate of 89.6%and an adsorption capacity of 112 mg·g^(-1)for CR dye.Furthermore,it retained 79%of its initial adsorption capacity after 10 cycles,demonstrating excellent regeneration performance.In summary,the synthesized N-PGA displays remarkable efficacy in the adsorption of CR dye in wastewater,opening up new possibilities for utilizing 3D porous graphene nanomaterials as efficient adsorbents in wastewater treatment.
基金supported by the National Key Research and Development Program of China(2022YFB3806800)the National Natural Science Foundation of China(22122811,22008209)the Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(2021SZ-TD008).
文摘The adsorptive separation of C_(2)H_(4)and C_(2)H_(6),as an alternative to distillation units consuming high energy,is a promising yet challenging research.The great similarity in the molecular size of C_(2)H_(4)and C_(2)H_(6)brings challenges to the regulation of adsorbents to realize efficient dynamic separation.Herein,we reported the enhancement of the kinetic separation of C_(2)H_(4)/C_(2)H_(6)by controlling the crystal size of ZnAtzPO_(4)(Atz=3-amino-1,2,4-triazole)to amplify the diffusion difference of C_(2)H_(4)and C_(2)H_(6).Through adjusting the synthesis temperature,reactant concentration,and ligands/metal ions molar ratio,ZnAtzPO4 crystals with different sizes were obtained.Both single-component kinetic adsorption tests and binary-component dynamic breakthrough experiments confirmed the enhancement of the dynamic separation of C_(2)H_(4)/C_(2)H_(6)with the increase in the crystal size of ZnAtzPO_(4).The separation selectivity of C_(2)H_(4)/C_(2)H_(6)increased from 1.3 to 98.5 with the increase in the crystal size of ZnAtzPO_(4).This work demonstrated the role of morphology and size control of adsorbent crystals in the improvement of the C_(2)H_(4)/C_(2)H_(6)kinetic separation performance.
基金financial support from the National Natural Science Foundation of China(22178154,22008094,21908082,21878133)Natural Science Foundation of Jiangsu Province(BK20190852,BK20190854)Natural Science Foundation for Jiangsu Colleges and Universities(19KJB530005).
文摘A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structure and the defective sites of h-BNNS not only are beneficial to the stabilization of Pt NPs but also favor the adsorption of aromatic sulfides.By employing Pt/h-BNNS with a Pt loading amount of 1.19 wt%as the active adsorbent and air as an oxidant,a 98.0%sulfur removal over dibenzothiophene(DBT)is achieved along with a total conversion of the DBT to the corresponding sulfones(DBTO_(2)).Detailed experiments show that the excellent desulfurization activity originates from the few-layered structure of h-BNNS and the high catalytic activity of Pt NPs.In addition,the OPADS system with Pt/h-BNNS as the active adsorbent shows remarkable stability in desulfurization performance with the existence of different interferents such as olefin,and aromatic hydrocarbons.Besides,the Pt/h-BNNS can be recycled 12 times without a significant decrease in desulfurization performance.Also,a process flow diagram is proposed for deep desulfurization of fuel oil and recovery of high value-added products,which would promote the industrial application of such OPADS strategy.
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”.
文摘Two major problems facing agriculture at present are soil pollution and the disposal of solid wastes generated during plant growth. The method of preparing biochar from solid wastes produced by plants is a means of maximizing the use of resources to combat the problem of soil pollution. In this study, we did not choose straw in the traditional sense but the waste branches from grape pruning, which has higher lignin cellulose, as the raw material. The biochar derived from grape branches pyrolyzed at 300˚C for two hours was utilized as a raw material to prepare modified biochar with varying concentrations of phosphoric acid. The adsorption performance and mechanism of Cd<sup>2 </sup> were explored through experiments involving different concentrations, addition amounts, reaction times, kinetic analyses, and isothermal adsorption tests. The findings indicated that the optimal adsorption of Cd<sup>2 </sup> occurred with a 20% phosphoric acid concentration, achieving the highest adsorption rate of 84.62%. At a dosage of 10 g/L, the maximum adsorption capacity reached 7.02 mg/g. The adsorption kinetics and isothermal adsorption of Cd<sup>2 </sup> on biochar modified with 0.2% phosphoric acid (0.2 PB) closely followed the pseudo-first-order kinetics model (R<sup>2</sup> > 0.98) and the Freundlich model (R<sup>2</sup> > 0.97), respectively. This suggests that the adsorption process involves both physical and chemical mechanisms. SEM and FTIR analyses revealed that phosphoric acid modification primarily increased the biochar’s specific surface area and enhanced certain original functional groups. The adsorption process predominantly involved rapid ion diffusion and chemical adsorption, as confirmed by kinetic analysis and isothermal adsorption model analysis. In summary, the adsorption efficiency of 0.2 PB significantly improved, showing potential and feasibility for heavy metal remediation in soil. This supports the environmentally friendly concept of “treating waste with waste”.
文摘Yala swamp wetland is the largest fresh water wetland ecosystem in Kenya supporting a broad biodiversity. It comprises of River Yala, the Yala swamp, Lakes Kanyaboli, Namboyo and Sare, and a portion of Lake Victoria neighboring the swamp. Approximately 2300 ha of land have been reclaimed and has been used for large-scale agriculture resulting in mass destruction of papyrus to create room for framing. Papyrus are known to be important in phytoremediation but despite this role information is limited, lacks supportive evidence and the empirical aspect on the levels of these pollutants in relation to the papyrus biomass is limited. The study is aimed at determining the effects of Cyperus papyrus on the water and sediment quality in Yala Swamp wetland. Six sampling sites were purposefully selected to monitor the variations of the physicochemical parameters (temperature, dissolved oxygen: DO, pH, biological oxygen demand: BOD, total suspended solids: TSS, turbidity, electrical conductivity: EC and total dissolved solids: TSS) and the levels selected nutrients (phosphorus and nitrates) in water and sediments as River Yala flows through Dominion Farms, Lake Sare which surrounded by Cyperus papyrus and finally into Lake Victoria. The samples were collected in triplicates during the wet and dry seasons (May and September 2015 respectively). The physicochemical parameters were measured in situ using a Hydrolab muiltimeter while the nutrients were analyzed using UV/Vis spectroscopy. Statistical analysis was done using SAS V9.0 software. The mean temperature was 26.19˚C ± 0.71˚C, DO: 3.72 ± 1.02 Mg/l, BOD: 3.9 ± 0.32 Mg/l, pH: 7.52 ± 0.17, TDS: 109 ± 86.33, EC: 173.26 ± 13.8 μS/cm, TSS: 12.42 ± 18.51 Mg/l and Turbidity: 12.29 ± 10.03 NTU. The values varied significantly at P 0.05 among all the sites. The results show that papyrus is useful in maintaining the required levels of physicochemical parameters. The study will assist in conservation of the papyrus to help phytoremediate pollutants from Dominion farms and the adjacent farms in order to have ecologically sound wetland.
文摘In this study, new nano spherical graphene modified with LDH(Layered Double Hydroxide) was prepared and used to remove As(Ⅲ) ion from aqueous solutions. At first, graphene oxide was synthesized from graphite using a well-known Hammer method. The obtained graphene oxide solution was sprayed in octanol solution under different temperatures and sprayed speed as influenced variables. The structure and physical characterization of synthesized spherical graphene oxide were determined by various techniques,including FT-IR, N_(2) adsorption–desorption, SEM, TEM, and EDX. In the next step, the hydrothermal method was applied to deposition LDH on the spherical graphene oxide. The synthesized spherical graphene modified by LDH was used to remove As(Ⅲ) as a toxic heavy metal ion. The effect of influenced variables including p H, contact time, amount of sorbent, and type eluent studied and the optimum values were as 8, 30, 50, and HCl(0.5 mol·L^(-1)), respectively. After optimization, the studied sorbent was shown a high adsorption capacity(149.3 mg·g^(-1)). The adsorption mechanism and kinetic models exhibited good agreement with the Langmuir isotherm and pseudo-second-order trends, respectively. Besides, the synthesized product was tested for seven times without significant loss in its sorption efficiency.
基金This work was supported by the National Natural Science Foundation of China(No.31972110)the National Key Research and Development Program of China(2018YFD0401102).
文摘Zearalenone is a mycotoxin produced by Fusarium species.It frequently contaminates cereals used for foods or animal feeds,especially deposited in crude corn oil.Certain amounts of zearalenone can be removed during refining processes.In this study,we studied the influence of activated carbon and six industial absorbents(zeolite,diatomite,attapulgite,perlite,montmorillonite and activated clay)on the elimination of zearalenone during bleaching process of corn oil and explored the absorption mechanism of activated carbon.Results showed that activated carbon had an excellent adsorption capacity of zearalenone compared with the other six industrial adsorbents.For activated carbon,a high removal rate of zearalenone(exceeding 83%)from heavily zearalenone-polluted corn oil was achieved and the removal rate of zearalenone was kept above 60%after five regeneration cycles.The research on the adsorption mechanism of activated carbon showed that Freundlich adsorption isotherm model and pseudo-second-order kinetic model could well described the adsorption process.The thermodynamic study demonstrated that adsorption process was spontaneous and exothermic.Fourier transform infrared spectroscopy and Raman spectroscopy further revealed that activated carbon was effectively combined with zearalenone viaπ-πinteraction.Thus,activated carbon is an efficient and suitable adsorbent to control the levels of zearalenone during bleaching process of corn oil.This study not only proposed a systematic research scheme for the mechanism study of activated carbon for the elimination of zearalenone in corn oil,but also provided the scientific basis for developing effective methods to eliminate zearalenone in refined vegetable oils.
基金the Liaoning Provincial Department of Education Fund(LJKMZ20220793 and LJKMZ20220795)the Applied Basic Research Program of Liaoning Science and Technology Department(2023JH2/101300231)。
文摘Synthesis of mixed matrix membranes(MMM)using carbon nanotubes(CNTs)has shown great prospects for achieving excellent selective separation because of its special structure.Nevertheless,the preparation of highly selective MMM faces challenges,which is attributed to the obstacles encountered by CNTs dispersion in polymer matrix and elimination of interface defects.A novel CNT-based composite decorated with metal–organic framework(MOF)was synthesized and applied to the preparation of MMM.MOF was post modified,and then carboxyl groups were inserted on the outer surface of CNTs.The synthetic MMM(Cu-MOF-en@MWCNT)not only has selective adsorption on dyes,but also has selective photodegradation on dyes.The method of using CNTs to wrap the outside of MOF has great potential in dye separation.The performance of MMM was further improved by decorating MOF on the filler to improve the selectivity to the designated dye.
基金funded by the 2019“Rare Earth and Coal Chemical Industry”Key Science and Technology Project of Inner Mongolia Autonomous Region of China(2019ZD017)the National Natural Science Foundation of China(21908197,22108248,22208305)。
文摘Carbon is a normally used adsorbent for removal of heavy metal ion in aqueous solutions,but the efficient adsorbent needs intensive modification by heteroatom doped or supported noble metals that cause severe pollution and easy leaching of active components during use.In this paper,the role of intrinsic defects on Hg^(2+)adsorption for carbon adsorbent was investigated.The maximum adsorbing capacity of defectrich carbon has been improved up to 433 mg·g^(-1)which is comparable to most of the modified carbon adsorbents via supported metal chloride or noble metal components.The basicity is increased with the content of defective sites and the strong chemical bonding can be formed via electron transformation between the defect sites with adsorbed Hg^(2+).The present study gives a direction to explore cheap and easily scale-up high-performance mercury adsorbents by simply tuning the intrinsic defective structure of carbon without the necessity to support metal or other organic compounds.
基金supported by the National Natural Science Foundation of China(51902007)。
文摘Water pollution regarding dyes and heavy metal ions is crucial facing the world.How to effectively separate these contaminants from water has been a key issue.Graphene oxide(GO)promises the greenwater world as a long-lasting spotlight adsorbent material and therefore,harnessing GO has been the research hotspot for over a decade.The state of GO as well as its surface functional groups plays an important role in adsorption.And the way of preparation and structural modification matters to the performance of GO.In this review,the significance of the state of existence of stock GO and surface functional groups is explored in terms of preparation,structural modification,and adsorption.Besides,various adsorbates for GO adsorption are also involved,the discussion of which is rarely established elsewhere.
基金the National Natural Science Foundation of China(Nos.21976069,21677062,21507155)。
文摘Porous polymer(pyrrolopyrrole)was successfully prepared via domino-ring-formation reaction.The chemical-physical properties of cyanided covalent triazine frameworks(CTF-CN)were characteriazed by fourier transform infrared spectra(FT-IR),scanning electron microscopy(SEM),nuclear magnetic resonance(NMR),specific surface area analyzer(BET)and thermogravimetric analysis(TGA),respectively.The experimental results of adsorption of chloranil(TCBQ)in aqueous solution indicated that CTF-CN exhibited distinctive adsorption capacity toward TCBQ owing to its large specific surface area.Specifically,the adsorption equilibrium of as-prepared polymer was executed within 5 h and the calculated adsorption capacity was 499.76 mg/g.Furthermore,the adsorption kinetics could be well defined with the linear pseudo-second-order model,which implies that the chemical interaction are relative important in the course of TCBQ removal.Finally,the current studies verify that CTF-CN has unique rigid and nano-porous framework structure,which can be employed for the treatment of a series of harmful aromatic substances.
基金funded by the National Natural Science Foundation of China(Grant No.42072147)the Qingdao Postdoctoral Science Foundation(Grant No.ZX20210070)。
文摘Because of the influence of hydrocarbons,especially adsorbed hydrocarbons,on the detection of cracked hydrocarbon(S2)and total organic carbon(TOC),the hydrogen index(HI)-based hydrocarbon generation model deviates from actual practice.In this study,the shale in the first member of the Qingshankou Formation in the central depression of the Songliao Basin,where in northeastern China,was taken as the research object and a correction method for S2 and TOC was established.By correcting the experimental results of different maturity samples,the actual hydrocarbon generation model has been revealed,the differences before and after correction compared,and the evolutionary characteristics of the adsorbed hydrocarbon content were clarified.The results show that the organic matter enters the hydrocarbon generation threshold at R_(o)-0.5% and reaches the hydrocarbon generation peak at R_(o)-1.0% and that the hydrocarbon generation process ends at R_(o)-1.3%.The hydrocarbon generation model established based on the measured values has a‘lag effect’compared to actual values,and this extends the hydrocarbon generation window of organic matter and delays the hydrocarbon generation peak.With the increase of maturity,adsorbed hydrocarbon content shows the characteristics of‘first increasing,then stabilizing,and then decreasing’,and reache s the most abundant stage at Roof 0.9%-1.3%.
基金supported by the National Natural Science Foundation of China(22008134)。
文摘To better understand the role of the-NH_(2)group in adsorption process of phenolic wastewaters,NH_(2)-functionalized MIL-53(Al)composites with activated carbon(NH_(2)-M(Al)@(B)AC)were prepared.The results showed that the-NH_(2)group could increase the mesopore volume for composites,which promotes mass transfer and full utilization of active sites,because hierarchical mesopore structure makes the adsorbent easier to enter the internal adsorption sites.Furthermore,the introduction of the-NH_(2)group can improve the adsorption capacity,decrease the activation energy,and enhance the interaction between the adsorbent and p-nitrophenol,demonstrating that the-NH_(2)group plays a crucial role in the adsorption of p-nitrophenol.The density functional theory calculation results show that the H-bond interaction between the-NH_(2)group in the adsorbent and the-NO_(2)in the p-nitrophenol(adsorption energy of -35.5 kJ·mol^(-1)),and base-acid interaction between the primary-NH_(2)group in the adsorbent and the acidic-OH group in the p-nitrophenol(adsorption energy of -27.3 kJ·mol^(-1))are predominant mechanisms for adsorption in terms of the NH_(2)-functionalized adsorbent.Both NH_(2)-functionalized M(Al)@AC and M(Al)@BAC composites exhibited higher p-nitrophenol adsorption capacity than corresponding nonfunctionalized composites.Among the composites,the NH_(2)-M(Al)@BAC had the highest p-nitrophenol adsorption capacity of 474 mg·g^(-1).
基金National Key Research and Development Program of China(Grant No.2019YFB1505000).
文摘Carbon monoxide(CO)is an impurity gas that can poison the precious metal catalysts of hydrogen fuel cells,so it is necessary to separate CO from hydrogen.In this paper,an isovolumetric impregnation method was developed to prepare Cu(I)-supported activated carbon(AC),which is simple and easy to industrialize.The prepared cuprous chloride CuCl/AC adsorbent displayed a high CO adsorption capacity of 82.1 cm^(3)/g and a high CO/H_(2) separation factor of 20 at 20 bar and 298 K.This material can adsorb and remove CO from CO/H_(2) mixed gas(5μL/L CO-balanced H_(2))to less than 0.2μL/L under dynamic flow conditions,and showed excellent regeneration performance.The results show that CuCl/AC is an effective adsorbent for separating trace CO in high-purity hydrogen.
基金Supported by the National Natural Science Foundation of China(42102154,41922015,42072147)China Postdoctoral Science Foundation(2021M690168)Postdoctoral Innovation Talent Support Program of Shandong Province(SDBX2021004).
文摘A quantitative evaluation model that integrates kerogen adsorption and clay pore adsorption of shale oil was proposed,and the evaluation charts of adsorption-swelling capacity of kerogen(Mk)and adsorbed oil capacity of clay minerals(Mc)were established,taking the 1st member of Cretaceous Qingshankou Formation in the northern Songliao Basin as an example.The model and charts were derived from swelling oil experiments performed on naturally evolved kerogens and adsorbed oil experiments on clays(separated from shale core samples).They were constructed on the basis of clarifying the control law of kerogen maturity evolution on its adsorption-swelling capacity,and considering the effect of both the clay pore surface area that occupied by adsorbed oil and formation temperature.The results are obtained in four aspects:(1)For the Qing 1 Member shale,with the increase of maturity,Mk decreases.Given Ro of 0.83%–1.65%,Mk is about 50–250 mg/g.(2)The clay in shale adsorbs asphaltene.Mc is 0.63 mg/m^(2),and about 15%of the clay pore surface is occupied by adsorbed oil.(3)In the low to medium maturity stages,the shale oil adsorption is controlled by organic matter.When Ro>1.3%,the shale oil adsorption capacity is contributed by clay pores.(4)The oil adsorption capacity evaluated on the surface at room temperature is 8%–22%(avg.15%)higher than that is held in the formations.The proposed evaluation model reveals the occurrence mechanisms of shale oils with different maturities,and provides a new insight for estimating the reserves of shale oil under formation temperature conditions.
基金Supported by the Sinopec Scientific Research Project(P21087-6).
文摘Based on the drilling, logging, experimental and testing data of Well PD1, a shallow normal-pressure shale gas well in the Laochangping anticline in southeastern Sichuan Basin, the shallow shale gas reservoirs of the Ordovician Wufeng Formation to Silurian Longmaxi Formation (Wufeng-Longmaxi) were investigated in terms of geological characteristics, occurrence mechanism, and adsorption-desorption characteristics, to reveal the enrichment laws and high-yield mechanism of shallow normal-pressure shale gas in complex structure areas. First, the shallow shale gas reservoirs are similar to the medium-deep shale gas reservoirs in static indicators such as high-quality shale thickness, geochemistry, physical properties and mineral composition, but the former is geologically characterized by low formation pressure coefficient, low gas content, high proportion of adsorbed gas, low in-situ stress, and big difference between principal stresses. Second, shallow shales in the complex structure areas have the gas occurrence characteristics including low total gas content (1.1-4.8 m3/t), high adsorbed gas content (2.5-2.8 m3/t), low sensitive desorption pressure (1.7-2.5 MPa), and good self-sealing. Third, the adsorbed gas enrichment of shales is mainly controlled by organic matter abundance, formation temperature and formation pressure: the higher the organic matter abundance and formation pressure, the lower the formation temperature and the higher the adsorption capacity, which is more beneficial for the adsorbed gas occurrence. Fourth, the shallow normal-pressure shale gas corresponds to low sensitive desorption pressure. The adsorbed gas can be rapidly desorbed and recovered when the flowing pressure is reduced below the sensitive desorption pressure. Fifth, the exploration breakthrough of Well PD1 demonstrates that the shallow complex structure areas with adsorbed gas in dominance can form large-scale shale reservoirs, and confirms the good exploration potential of shallow normal-pressure shale gas in the margin of the Sichuan Basin.
基金Jilin Province Science and Technology Development Program,Grant/Award Numbers:20180101030JC,20190201270JC,20200201001JCNational Natural Science Foundation of China,Grant/Award Numbers:21633008,21673221,21875243,U1601211+1 种基金Research Innovation Fund,Grant/Award Number:DNL202010Special Funds for Guiding Local Scientific and Technological Development by the Central Government,Grant/Award Number:2020JH6/10500021。
文摘CO impurity-induced catalyst deactivation has long been one of the biggest challenges in proton-exchange membrane fuel cells,with the poisoning phenomenon mainly attributed to the overly strong adsorption on the catalytic site.Here,we present a mechanistic study that overturns this understanding by using Rh-based single-atom catalysis centers as model catalysts.We precisely modulated the chelation structure of the Rh catalyst by coordinating Rh with C or N atoms,and probed the reaction mechanism by surface-enhanced Raman spectroscopy.Direct spectroscopic evidence for intermediates indicates that the reactivity of adsorbed OH^(*),rather than the adsorption strength of CO^(*),dictates the CO electrocatalytic oxidation behavior.The RhN_(4)sites,which adsorb the OH^(*)intermediate more weakly than RhC4 sites,showed prominent CO oxidation activity that not only far exceeded the traditional Pt/C but also the RhC4 sites with similar CO adsorption strength.From this study,it is clear that a paradigm shift in future research should be considered to rationally design high-performance CO electro-oxidation reaction catalysts by sufficiently considering the water-related reaction intermediate during catalysis.
基金the support from the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(Nos.22008170,22278307,22222808,21978200)+1 种基金the Haihe Laboratory of Sustainable Chemical Transformationsthe Tianjin Research Innovation Project for Postgraduate Students(2022B KYZ035)。
文摘Water electrolysis,a process for producing green hydrogen from renewable energy,plays a crucial role in the transition toward a sustainable energy landscape and the realization of the hydrogen economy.Oxygen evolution reaction(OER)is a critical step in water electrolysis and is often limited by its slow kinetics.Two main mechanisms,namely the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM),are commonly considered in the context of OER.However,designing efficient catalysts based on either the AEM or the LOM remains a topic of debate,and there is no consensus on whether activity and stability are directly related to a certain mechanism.Considering the above,we discuss the characteristics,advantages,and disadvantages of AEM and LOM.Additionally,we provide insights on leveraging the LOM to develop highly active and stable OER catalysts in future.For instance,it is essential to accurately differentiate between reversible and irreversible lattice oxygen redox reactions to elucidate the LOM.Furthermore,we discuss strategies for effectively activating lattice oxygen to achieve controllable steady-state exchange between lattice oxygen and an electrolyte(OH^(-)or H_(2)O).Additionally,we discuss the use of in situ characterization techniques and theoretical calculations as promising avenues for further elucidating the LOM.
基金supported by the National Natural Science Foundation of China(No.51472220 and No.51872265)Collaborative Innovation Major Special Project of Zhengzhou(No.20XTZX12025)。
文摘To meet the emission standard of nitrogen oxides(NOx)in the flue gas of batch furnaces through dry adsorption,a calcium-silica inorganic adsorbent was prepared with limestone and quartz as raw materials.Sample Cu-BTC 1#was obtained by solvothermal synthesis,drying and purification in vacuum at 120℃using trimesic acid(H3BTC)and copper nitrate trihydrate(Cu(NO_(3))2·3H_(2)O)as raw materials;likewise,sample Cu-BTC 3#was obtained at 200℃.Sample Cu-BTC 2#was obtained by hydrothermal synthesis,drying and purification in air(metal-organic frameworks,1,3,5-benzene tricarboxylic acid copper).The two types of materials were tested in terms of the NO_(2) adsorption,and then the specific surface area,pore volume,NO_(2) adsorption performance,phase composition,microstructure and thermal stability of the adsorbent materials were exploredvia N_(2) physical adsorption-desorption,SEM,XRD and TG characterization.The results show that:(1)the Cu-BTC samples have higher adsorption capacity than the calcium-silica adsorbent,in which sample Cu-BTC 3#has the largest specific surface area and pore volume,thus adsorption capacity for NO_(2);(2)the calcium-silica adsorbent has better thermal stability and lower total mass loss during the entire process than the Cu-BTC samples;sample Cu-BTC 2#has the best thermal stability among the three Cu-BTC samples,and the metal Cu active sites of the Cu-BTC samples can be exposed at least above 150℃.