Grapevine-like high entropy oxide composites boost high-performance lithium sulfur batteries as bifunctional interlayers

Lithium-sulfur batteries(LSBs)with high energy densities have been demonstrated the potential for energy-intensive demand applications.However,their commercial applicability is hampered by hysteretic electrode reaction kinetics and the shuttle effect of lithium polysulfides(LiPSs).In this work,an interlayer consisting of high-entropy metal oxide(Cu_(0.7)Fe_(0.6)Mn_(0.4)Ni_(0.6)Sn_(0.5))O_(4) grown on carbon nanofibers(HEO/CNFs)is designed for LSBs.The CNFs with highly porous networks provide transport pathways for Li^(+) and e^(-),as well as a physical sieve effect to limit LiPSs crossover.In particular,the grapevine-like HEO nanoparticles generate metal-sulfur bonds with LiPSs,efficiently anchoring active materials.The unique structure and function of the interlayer enable the LSBs with superior electrochemical performance,i.e.,the high specific capacity of 1381 mAh g^(-1) at 0.1 C and 561 mAh g^(-1) at 6 C.This work presents a facile strategy for exploiting high-performance LSBs.

Toward Next-Generation Heterogeneous Catalysts:Empowering Surface Reactivity Prediction with Machine Learning

Heterogeneous catalysis remains at the core of various bulk chemical manufacturing and energy conversion processes,and its revolution necessitates the hunt for new materials with ideal catalytic activities and economic feasibility.Computational high-throughput screening presents a viable solution to this challenge,as machine learning(ML)has demonstrated its great potential in accelerating such processes by providing satisfactory estimations of surface reactivity with relatively low-cost information.This review focuses on recent progress in applying ML in adsorption energy prediction,which predominantly quantifies the catalytic potential of a solid catalyst.ML models that leverage inputs from different categories and exhibit various levels of complexity are classified and discussed.At the end of the review,an outlook on the current challenges and future opportunities of ML-assisted catalyst screening is supplied.We believe that this review summarizes major achievements in accelerating catalyst discovery through ML and can inspire researchers to further devise novel strategies to accelerate materials design and,ultimately,reshape the chemical industry and energy landscape.

Adsorption of sodium oleate at the microfine hematite/aqueous solution interface and its consequences for flotation

The adsorption of sodium oleate(NaOL)at the microfine hematite/aqueous solution interface was investigated in this paper.Experimental research indicated that negative effects stemmed from the dissolution of the microfine hematite(D50=19.21μm)could be effectively eliminated via the appropriate dosage of NaOL at alkali pH conditions.Solution chemistry calculation and adsorption test results indicated that RCOO
and(RCOO)_(2)^(2-) ions were responsible for microfine hematite flotation at pH 8.2.Zeta potential and FTIR measurements confirmed the co-adsorption of molecular and ionic oleate species occurred at pH 8.2.X-ray photoelectron spectroscopy(XPS)results further indicated that oleate species interacted with hematite surfaces mainly through chemisorption,giving rise to molecule/colloid formation of oleate and Fe―OL complex compound.Time-of-flight secondary ion mass spectrometry(ToF-SIMS)results demonstrated that oleate species adsorbed onto the hematite surfaces with a thickness of a few nanometers.Furthermore,the normalized peak intensity of C4H7+ions on the hematite sample at pH 8.2 increased remarkably comparing with corresponding result of hematite sample at pH 6.8.The new findings of the present study well revealed the dissolution of microfine hematite and the pH effects on the hematite flotation,as well as the adsorption characteristics of oleate species.

Assessing Lead Removal from Contaminated Water Using Solid Biomaterials: Charcoal, Coffee, Tea, Fishbone, and Caffeine

Previous research has documented that solid biomaterials such as charcoal or waste coffee and tea have been used to remove heavy metals from contaminated aqueous solutions through adsorption. However, these studies used very low heavy metal concentrations between 10 to 100 ppm. Recently published research work reported that extracts of edible plants and fruits were able to effectively remove lead from contaminated aqueous solution. This paper evaluates the ability of charcoal, un-brewed coffee and tea, fishbone, and caffeine to remove lead from contaminated aqueous solutions. The order of lead removal from 1300 ppm of lead solution is Charcoal (100%) > Tea (97%) > Coffee Ground (88%) > Instant Coffee (83.5%) > Coffee Bean (82%) > Fishbone (76%) > Caffeine (1.3%). These results clearly demonstrate that not all solid biomaterials can adsorb lead and that caffeine, a component of coffee and tea does not participate in the removal of lead from contaminated solutions. Furthermore, the results suggest that two possible processes may be involved in the reactions presented here: adsorption of lead by the solid substrates and precipitation of lead by the solubilized biochemical components of the substrates.

Thermodynamics of Cr(Ⅵ) adsorption on strong alkaline anion exchange fiber

Removal of Cr（VI） from aqueous solution by strong alkaline anion exchange fiber （SAAEF） was achieved using batch adsorption experiments. The effect of contact time, initial Cr（VI） concentration and pH was investigated. The results showed that the maximum adsorption capacity of SAAEF was 187.7 mg/g at pH=1.0. The adsorption capacity increased with Cr（VI） concentration but decreased with pH value when pH〉1.0. Adsorption isotherms at various temperatures were obtained. Langmuir, Freundlich, Dubinin-Radushkevich and Temkin models were adopted and the equilibrium data fitted best with the Langmuir isotherm. The constants of these models indicated that the adsorption process involved both chemisorption and physisorption. The values of thermodynamic parameters, including DH, DG and DS, suggested that the adsorption of Cr（VI） on SAAEF was a spontaneous, entropy-driven and endothermic process. Q（iso） was not a constant value, which indicated an inhomogenous energy distribution on SAAEF.

Effect of temperature on floatability and adsorption behavior of fine wolframite with sodium oleate

The influence of pulp temperature on the floatability and adsorption behavior of fine wolframite with sodium oleate was investigated by microflotation experiments, electric conductivity tests, adsorption measurements, and FT-IR analysis. Microflotation results show that fine wolframite with sodium oleate exhibits a good floatability at pH 8–9. Electric conductivity tests indicate that the high temperature enhances the ionization degree and electric mobility of oleate species, then the flotation recovery of fine wolframite and the adsorption amount of sodium oleate are observed to increase with the rise in pulp temperature. The results of adsorption experiments are found to meet Freundlich isotherms successfully, and the isosteric enthalpy （ΔH^Θ） is in conformity with the chemical bonding. The changes in FT-IR analysis provide sufficient evidence that sodium oleate interacts with the metal cations of wolframite surface, and the increase in pulp temperature clearly promotes the chemisorption intensity. These findings will be beneficial to strengthen the flotation behavior of fine wolframite.

ADSORPTION OF 2,4-DICHLOROPHENOL IN AQUEOUS SOLUTION ONTO ADSORPTION RESIN MODIFIED BY N-ACETYLANILINE

A hypercrosslinked adsorption resin （ZH-05） modified by N-acetylaniline in the post crosslinking process was prepared. The adsorption properties of ZH-05 toward 2,4-dichlorophenol in comparison with granular activated carbon （GAC） and Amberlite XAD-4 were observed. The present study mainly focuses on the static equilibrium adsorption behaviors, desorption profiles and the proof of chemisorption. The results show that the Langmuir equation can give a perfect fitting to experimental data, and high temperature was favorable for adsorption of 2,4-dichlorophenol on ZH-05. A related equation was used to correlate the amount of chemisorption and the suppositionai chemisorption equilibrium concentration of adsorbate in aqueous solution. The adsorption capacities from different ranges of temperature and the static desorption experiment both reveal the same conclusion, i.e., the adsorption of 2,4-dichlorophenol from water on ZH-05 is a coexistent process of physical adsorption and chemical transition as on GAC.

Revalorization of CO2 for methanol production via ZnO promoted carbon nanofibers based Cu-ZrO2 catalytic hydrogenation

A series of novel carbon nanofibers(CNFs)based Cu-ZrO2 catalysts were synthesized by deposition precipitation method.To investigate the influence of promoter,catalysts were loaded with 1,2,3 and 4 wt%ZnO and characterized by ICP-OES,HRTEM,BET,N2O chemisorption,TPR,XPS and CO2-TPD techniques.The results revealed that physicochemical properties of the catalysts were strongly influenced by incorporation of ZnO to the parent catalyst.Copper surface area(SCu)and dispersion(DCu)were slightly decreased by incorporation of ZnO promoter.Nevertheless,SCuand DCuwere remarkably decreased when ZnO content was exceeded beyond 3 wt%.The catalytic performance was evaluated by using autoclave slurry reactor at a pressure and temperature of 30 bar and 180℃,respectively.The promotion of CuZrO2/CNFs catalyst with 3 wt%of ZnO enhanced methanol synthesis rate from 32 to 45 g kg^-1 h^-1.Notably,with the ZnO promotion the selectivity to methanol was enhanced to 92%compared to 78%of the un-promoted Cu-ZrO2/CNFs catalyst at the expense of a lowered CO2 conversion.In addition,the catalytic activity of this novel catalyst system for CO2 hydrogenation to methanol was compared with the recent literature data.

Enabling Multi-Chemisorption Sites on Carbon Nanofibers Cathodes by an In-situ Exfoliation Strategy for High-Performance Zn–Ion Hybrid Capacitors

Carbon nanofibers films are typical flexible electrode in the field of energy storage,but their application in Zinc-ion hybrid capacitors(ZIHCs)is limited by the low energy density due to the lack of active adsorption sites.In this work,an in-situ exfoliation strategy is reported to modulate the chemisorption sites of carbon nanofibers by high pyridine/pyrrole nitrogen doping and carbonyl functionalization.The experimental results and theoretical calculations indicate that the highly electronegative pyridine/pyrrole nitrogen dopants can not only greatly reduce the binding energy between carbonyl group and Z n2+by inducing charge delocalization of the carbonyl group,but also promote the adsorption of Zn2+by bonding with the carbonyl group to form N–Zn–O bond.Benefit from the multiple highly active chemisorption sites generated by the synergy between carbonyl groups and pyridine/pyrrole nitrogen atoms,the resulting carbon nanofibers film cathode displays a high energy density,an ultralong-term lifespan,and excellent capacity reservation under commercial mass loading(14.45 mg cm-2).Particularly,the cathodes can also operate stably in flexible or quasi-solid devices,indicating its application potential in flexible electronic products.This work established a universal method to solve the bottleneck problem of insufficient active adsorption sites of carbon-based ZIHCs.Imoproved should be changed into Improved.

Engineering vacancies for solar photocatalytic applications

In contrast to the exploration of novel photocatalytic materials,vacancy engineering of traditionalphotocatalysts comprising earth‐abundant elements represents an effective method for enhancingphotocatalytic performance without introducing alien elements.This minireview analyzes the latestprogress in engineering vacancies in photocatalysts,remarks on state‐of‐the‐art characterizationtechniques for vacancies,and reviews the formation chemistry and fundamental benefits of anionand cation vacancies in typical photocatalysts.Although knowledge of these vacancies is increasing,challenges remain in this field,and possible further research is therefore also discussed.

Study on Chemisorption and Desorption of Hydrogen and Nitrogen on Ru-based Ammonia Synthesis Catalyst

The effects of promoters K, Ba, Sm on the chemisorption and desorption of hydrogen and nitrogen, dispersion of metallic Ru. and catalytic activity of active carbon (AC) supported ruthenium catalyst for ammonia synthesis have been studied by means of pulse chromatography, temperature-programmed desorption, and activity test. Promoters K, Ba and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly, and particularly, potassium exhibited the best promotion on the activity because of the strong electronic donation to metallic Ru. Much higher activity can be obtained for Ru/AC catalyst with binary or triple promoters. The activity of Ru/AC catalyst is dependent on the adsorption of hydrogen and nitrogen. The high activity of catalyst could be ascribed to strong dissociation of nitrogen on the catalyst surface. Strong adsorption of hydrogen would inhibit the adsorption of nitrogen, resulted in decrease of the catalytic activity. Ru/AC catalyst promoted by Sm2O3 shows the best dispersion of metallic Ru, since the partly reduced SmOx on the surface modifies the morphology of active sites and favors the dispersion of metallic Ru. The activity of Ru/AC catalysts is in accordance to the corresponding amount of nitrogen chemisorption and the desorption activation energy of nitrogen. The desorption activation energy for nitrogen decreases in the order of Ru>Ru-Ba>Ru-Sm>Ru-Ba-Sm>Ru-K>Ru-K-Sm>Ru-K-Ba>Ru-K-Ba-Sm, just opposite to the order of catalytic activity, suggesting that the ammonia synthesis over Ru-based catalyst is controlled by the step of dissociation of nitrogen.

ADSORPTION BEHAVIOR OF PHENOLIC COMPOUNDS ONTO POLYMERIC ADSORBENTS MODIFIED WITH 2-CARBOXYBENZOYL GROUPS

Two hypercrosslinked polymeric adsorbents （ZH-01 and Amberlite XAD-4 resin） were employed to remove three kinds of phenolic compounds including phenol, 4-nitrophenol and 2,4-dinitrophenol from aqueous solutions. The study was focused on the static equilibrium adsorption behavior, the column dynamic adsorption and desorption profiles. The Freundlich model gave a perfect fitting to the isotherm data. The adsorbing capacities for these three compounds on ZH-01 were higher than those on Amberlite XAD-4 within the temperature range 288-318 K, which was attributed to the large micropore area and 2-carboxybenzoyl functional groups on the network of ZH-01 resin. The adsorption for phenol and 4- nitrophenol on ZH-01 was a physical adsorption process, while for 2,4-dinitrophenol it was a coexistence process of physical adsorption and chemisorption＇s transitions. The column test showed the advantages of ZH-01 in the dynamic adsorption processes of phenolic compounds. Being used as the desorption reagent, sodium hydroxide solution showed an excellent performance.

Adsorbability of Mycobacterium phlei on hematite surface

The adsorption of microorganisms on the mineral surface is the base of microorganisms that are considered as mineral processing reagents. The principles of the use of a highly hydrophobic and negatively charged bacterium, Mycobacterium phlei, as a flocculating-flotating agent for finely divided hematite were investigated. The flocculating-floating recovery is strongly dependent on the pH and the dosage of the bacterium. Generally the pH should be controlled over the range of 5.5-7, and the dosage should be controlled about 16 mg/L. The infrared spectrometry analysis indicates that the six functional groups of M. phlei, substituted aromatic compound groups, -（CH2） n-groups, -CH2（-CH3） groups, carbonyl groups, aromatic hydrocarbon groups, and carboxyl groups, are on the hematite surface, among which the first five ones contribute physical adsorption and only the carboxyl groups provide chemisorption. Microscopic analysis reveals that the dimensions and tight aggregation degree of the flocs of hematite particles formed by M. phlei are also impacted by the pH and the content of M. phlei in flotation.

ADSORPTION CHARACTERISTICS OF CHLOROPHENOLS FROM AQUATIC SYSTEMS BY HYPERCROSSLINKED RESINS MODIFIED WITH BENZOYL GROUP

A hypercrosslinked polymeric adsorbent （ZH-03） for adsorbing and removing chlorophenolic compounds from their aqueous solutions was studied, including the static adsorption. The equilibrium adsorption data were fit to Freundlich adsorption isothermic models to evaluate the model parameters. Thermodynamic studies on the adsorption of chlorophenolic compounds on ZH-03 indicated that there were chemisorption transitions for 2,4,6-trichlorophenol and physical adsorption processes for 2-chlorophenol and 2,6-chlorophenol, and ZH-03 showed the homogeneous nature of the adsorbent surface. Column adsorption for chlorophenols wastewater shows the advantages of the ZH-03 adsorbent for adsorbing the following chlorophenolic compounds as 2-chlorophenol, 2,6-dichlorophenol and 2,4,6-trichlorophenol. Sodium hydroxide was used for desorpting chlorophenols from ZH-03 and showed excellent performance.

Nitrogen-rich azoles as trifunctional electrolyte additives for high-performance lithium-sulfur battery

Rechargeable lithium-sulfur(Li-S)batteries are considered one of the most promising energy storage techniques owing to the high theoretical energy density.However,challenges still remain such as the shuttle effect of lithium polysulfides(LPSs)and the instability of lithium metal anode.Herein,we propose to use nitrogen-rich azoles,i.e.,triazole(Ta)and tetrazole(Tta),as trifunctional electrolyte additives for Li-S batteries.The azoles afford strong lithiophilicity for the chemisorption of LPSs.The density functional theory and experimental analysis verify the presence of Li bonds between the azoles and LPSs.The azoles can also interact with lithium salt in the electrolyte,leading to increase ionic conductivity and lithiumion transference number.Moreover,the azoles render particle-like lithium deposition on the lithium metal anode,leading to superlong cycling of a Li symmetric cell.The Li-S batteries with Ta and Tta exhibit the initial discharge capacity of 1425.5 and 1322.2 m Ah g^(-1),respectively,at 0.2 C rate,and promising cycling stability.They also enable enhanced cycling performance of a Li-organosulfide battery.

Research of the behaviour of O chemisorption on the （110） surface of Rhx-Pt1-x alloy

An atomic group model of the disordered binary alloy Rhx-Pt1-x has been constructed to investigate surface segregation. According to the model, we have calculated the electronic structure of the Rhx-Pt1-x alloy surface by using the recursion method when O atoms are adsorbed on the Rhx-Pt1-x （110） surface under the condition of coverage 0.5. The calculation results indicate that the chemical adsorption of O changes greatly the density of states near the Fermi level, and the surface segregation exhibits a reversal behaviour. In addition, when x 〈 0.3, the surface on which O is adsorbed displays the property of Pt; whereas when x 〉 0.3 it displays the property of Rh.

Adsorption of Fe on GaAs（100）Surface

The adsorption of one monolayer Fe atoms on an ideal GaAs (100) surface is studied by using the self-consistent tight-binding linear muffin-tin orbital method. The Fe adatom chemisorption on Ga- and As-terminatedsurface are considered separately. A monolayer of S atoms is used to saturate the dangling bonds on one of the supercellsurfaces. Energies of adsorption systems of an Fe atom on different sites are calculated, and the charge transfers areinvestigated. It is found that Fe-As interaction is stronger than Fe-Ga interaction and Fe atoms prefer to be adsorbed onthe As-terminated surface. It is possible for the adsorbed Fe atoms to sit below the As-terminated surface resulting inan Fe-Ga-As mixed layer. The layer projected density states are calculated and compared with that of the clean surface.

Water Gas Shift Reaction： A Monte Carlo Simulation

The water gas shift （WGS） reaction is reacts with water on a catalytic surface a process of industrial importance to form CO2 and H2. We study this In this reaction carbon monoxide reaction with thermal （Langmuir- Hinshelwood） and non-thermal （precursor and Eley-Rideal） reaction mechanisms using the techniques of Monte Carlo computer simulation. The details of surface coverages and production rates are given as a function of CO partial pressure. The diffusion of species on the surface as well as their desorption from the surface is also introduced to include temperature effects. The phase diagrams of the system have been drawn to observe the behaviour of reacting species on the surface. The study reveals that the production rates are higher for non-thermal precursor mechanism and are in agreement with the experimental finding.

Effect of Ca/Mg molar ratio on the calcium-based sorbents

Steelmaking industry faces urgent demands for both steel slag utilization and CO_(2)abatement.Ca and Mg of steel slag can be extracted by acid solution and used to prepare sorbents for CO_(2)capture.In this work,the calcium-based sorbents were prepared from stainless steel slag leachate by co-precipitation,and the initial CO_(2)chemisorption capacity of the calcium-based sorbent prepared from steel slag with the Ca and Mg molar ratio of 3.64:1 was 0.40 g/g.Moreover,the effect of Ca/Mg molar ratio on the morphology,structure,and CO_(2)chemisorption capacity of the calcium-based sorbents were investigated.The results show that the optimal Ca/Mg molar ratio of sorbent for CO_(2)capture was4.2:1,and the skeleton support effect of MgO in calcium-based sorbents was determined.Meanwhile,the chemisorption kinetics of the sorbents was studied using the Avrami-Erofeev model.There were two processes of CO_(2)chemisorption,and the activation energy of the first stage(reaction control)was found to be lower than that of the second stage(diffusion control).

A New Activation Method for Electroless Metal Plating: Palladium Laden via Bonding with Self-Assembly Monolayers

A new activation method has been developed for electroless copper plating on silicon wafer based on palladium chemisorption on SAMs of APTS without SnCl2 sensitization and roughening condition. A closely packed electroless copper film with strong adhesion is successfully formed by AFM observation. XPS study indicates that palladium chemisorption occurred via palladium chloride bonding to the pendant amino group of the SAMs.