The exposed and transformed groups of fibrous brucite,wollastonite,chrysotile asbestos,sepiolite,palygorskite,clinoptilolite,crocidolite and diatomaceous earth mineral materials are analyzed by IR spectra after acid a...The exposed and transformed groups of fibrous brucite,wollastonite,chrysotile asbestos,sepiolite,palygorskite,clinoptilolite,crocidolite and diatomaceous earth mineral materials are analyzed by IR spectra after acid and alikali etching,strong mechanical and polarity molecular interaction.The results show the active sites concentrate on the ends in stick mineral materials and on the defect or hole edge in pipe mineral materials.The inside active site of mineral materials plays a main role in small molecular substance.The shape of minerals influence their distribution and density of active site.The strong mechanical impulsion and weak chemical force change the active site feature of minerals,the powder process enables minerals exposed more surface group and more combined types.The surface processing with the small polarity molecular or the brand of middle molecular may produce ionation and new coordinate bond,and change the active properties and level of original mineral materials.展开更多
MXene quantum dots(MQDs)offer wide applications owing to the abundant surface chemistry,tunable energy-level structure,and unique properties.However,the application of MQDs in electrochemical energy conversion,includi...MXene quantum dots(MQDs)offer wide applications owing to the abundant surface chemistry,tunable energy-level structure,and unique properties.However,the application of MQDs in electrochemical energy conversion,including hydrogen evolution reaction(HER),remains to be realized,as it remains a challenge to precisely control the types of surface groups and tune the structure of energy levels in MQDs,owing to the high surface energy-induced strong agglomeration in post-processing.Consequently,the determination of the exact catalytically active sites and processes involved in such an electrocatalysis is challenging because of the complexity of the synthetic process and reaction conditions.Herein,we demonstrated the spontaneous evolution of the surface groups of the Ti_(2)CT_(x)MQDs(x:the content of O atom),i.e.,replacement of the-Cl functional groups by O-terminated ones during the cathode reaction.This process resulted in a low Gibbs free energy(0.26 eV)in HER.Our steady Ti_(2)CO_(x)/Cu_(2)O/Cu foam systems exhibited a low overpotential of 175 mV at 10 mA cm^(-2)in 1 M aq.KOH,and excellent operational stability over 165 h at a constant current density of-10 mA cm^(-2).展开更多
By constructing counterexamples,the authors show that the fixed subgroups are not compressed in direct products of free and surface groups,and hence negate a conjecture in[Zhang,Q.,Ventura,E.and J.Wu,Fixed subgroups a...By constructing counterexamples,the authors show that the fixed subgroups are not compressed in direct products of free and surface groups,and hence negate a conjecture in[Zhang,Q.,Ventura,E.and J.Wu,Fixed subgroups are compressed in surface groups,Internat.J.Algebra Comput.,25,2015,865–887].展开更多
Biochar(BC)are widely used as highly efficient adsorbents to alleviate aromatics-based contaminants due to their ease of preparation,wide availability,and high sustainability.The surface properties of BCs usually vary...Biochar(BC)are widely used as highly efficient adsorbents to alleviate aromatics-based contaminants due to their ease of preparation,wide availability,and high sustainability.The surface properties of BCs usually vary greatly due to their complex chemical constituents and different preparation processes and are reflected in the values of parameters such as the specific surface area(SSA),pore volume/size,and surface functional groups(SFGs).The effects of SSA and pore volume/size on the adsorption of aromatics have been widely reported.However,the corresponding mechanisms of BC SFGs towards aromatics adsorption remains unclear as the compositions of the SFGs are usually complex and hard to determine.To address in this gap in the literature,this review introduces a new perspective on the adsorption mechanisms of aromatics.Through collecting previously-reported results,the parameters log P(logarithm of the Kow),polar surface area,and the positive/negative charges were carefully calculated using Chem Draw3D,which allowed the hydrophobicity/hydrophilicity properties,electron donor-acceptor interactions,Hbonding,and electrostatic interactions between SFGs and aromatics-based contaminates to be inferred intuitively.These predictions were consistent with the reported results and showed that tailor-made BCs can be designed according to the molecular weights,chemical structures,and polarities of the target aromatics.Overall,this review provides new insight into predicting the physicochemical properties of BCs through revealing the relationship between SFGs and adsorbates,which may provide useful guidance for the preparing of highly-efficient,functional BCs for the adsorption of aromatics.展开更多
The activated carbon with high surface area was prepared by KOH activation.It was further modified by H2SO4 and HNO3 to introduce more surface functional groups.The pore structure of the activated carbons before and a...The activated carbon with high surface area was prepared by KOH activation.It was further modified by H2SO4 and HNO3 to introduce more surface functional groups.The pore structure of the activated carbons before and after modification was analyzed based on the nitrogen adsorption isotherms.The morphology of those activated carbons was characterized using scanning electronic microscopy （SEM）.The surface functional groups were determined by Fourier transform infrared spectroscopy （FTIR）.The quantity of those groups was measured by the Boehm titration method.Cr（VI） removal by the activated carbons from aqueous solution was investigated at different pH values.The results show that compared with H2SO4,HNO3 destructs the original pore of the activated carbon more seriously and induces more acidic surface functional groups on the activated carbon.The pH value of the solution plays a key role in the Cr（VI） removal.The ability of reducing Cr（VI） to Cr（III） by the activated carbons is relative to the acidic surface functional groups.At higher pH values,the Cr（VI） removal ratio is improved by increasing the acidic surface functional groups of the activated carbons.At lower pH values,however,the acidic surface functional groups almost have no effect on the Cr（VI） removal by the activated carbon from aqueous solution.展开更多
The thermal deactivation of diesel soot particles exerts a significant influence on the control strategy for the regeneration of diesel particulate filters(DPFs).This work focused on the changes in the surface functio...The thermal deactivation of diesel soot particles exerts a significant influence on the control strategy for the regeneration of diesel particulate filters(DPFs).This work focused on the changes in the surface functional groups,carbon chemical state,and graphitization degree during thermal treatment in an inert gas environment at intermediate temperatures of 600℃,800℃,and 1000℃ and explore the chemical species that were desorbed from the diesel soot surface during thermal treatment using a thermogravimetric analyser coupled with a gas-chromatograph mass spectrometer(TGA-GC/MS).The surface functional groups and carbon chemical statewere characterized using Fourier transform infrared spectroscopy(FT-IR)and X-ray photoelectron spectroscopy(XPS).The graphitization degree was evaluated by means of Raman spectroscopy(RS).The concentrations of aliphatic C–H,C–OH,C=O,and O–C=O groups are reduced for diesel soot and carbon black when increasing the thermal treatment temperature,while the sp^(2)/sp^(3) hybridized ratio and graphitization degree enhance.These results provide comprehensive evidence of the decreased reactivity of soot samples.Among oxygenated functional groups,the percentage reduction during thermal treatment is the largest for the O–C=O groups owing to its worst thermodynamic stability.TGA-GC/MS results show that the aliphatic and aromatic chains and oxygenated species would be desorbed from the soot surface during 1000℃ thermal treatment of diesel soot.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
FeO;supported on activated carbon(AC) has been shown to be an ideal catalyst for catalytic wet peroxide oxidation(CWPO) due to its high CWPO reaction activity and stability. Although there have been some studies on th...FeO;supported on activated carbon(AC) has been shown to be an ideal catalyst for catalytic wet peroxide oxidation(CWPO) due to its high CWPO reaction activity and stability. Although there have been some studies on the mechanism of Fe/AC catalysis in CWPO, the specific contribution of each component(surface oxygen groups and FeOxon AC) inside an Fe/AC catalyst and their corresponding reaction mechanism remain unclear, and the reaction stability of CWPO catalysts has rarely been discussed. Then the optimal CWPO catalyst in our laboratory, 3%Fe/AC, was selected.(1) By removing certain components on the AC through heat treatment, its contribution to the reaction and the corresponding reaction mechanism were investigated. With the aid of temperature-programmed desorption–mass spectrometry(TPD–MS) and the CWPO reaction, the normalized catalytic contributions of components were shown to be: 37.3%(carboxylic groups), 5.3%(anhydride), 19.3%(ether/hydroxyl),-71.4%(carbonyl groups) and 100%(FeOx),respectively. DFT calculation and EPR analysis confirmed that carboxylic groups and Fe_(2)O_(3) are able to activate the H_(2)O_(2) to generate·OH.(2) The catalysts at were characterized at different reaction times(0 h, 450 h, 900 h, 1350 h, and 1800 h) by TPD–MS and M?ssbauer spectroscopy. Results suggested that the number of carboxylic goups gradually increased and the size of paramagnetic Fe_(2)O_(3) particle crystallites gradually increased as the reactions progressed. The occurrence of strong interactions between metal oxides and AC was also confirmed. Due to these effects, the strong stability of 3%Fe/AC was further improved. Therefore, the reasons for the high activity and strong stability of 3%Fe/AC in CWPO were clearly shown. We believe that this work provides an idea of the removal of cresols from wastewater into the introduction to show the potential applications of CWPO.展开更多
The oxidation heat of coal is the direct reason leading to coal spontaneous combustion. When coal is exposed in oxygen atmosphere, the physical adsorption and chemisorption happened, and then which resulting chemical ...The oxidation heat of coal is the direct reason leading to coal spontaneous combustion. When coal is exposed in oxygen atmosphere, the physical adsorption and chemisorption happened, and then which resulting chemical reaction followed heat between coal and oxygen. Owing to the complexity and uncertain of molecular structure of coal,it was only reduced that bridge bonds, side chains and O 2 containing functional groups in coal may be prone to oxidation in last year, but not to deeply investigate into the structures and the type of the active radicals. In this paper, according to the last achievements in coal structure research, the hypomethylether bond, hypoalkyl bond of α carbon atom with hydroxyl and α carbon atom with hypomethy side chain and hypomethyl bonds linking up two aromatic hydrocarbon in bridge bonds, and methoxy,aldehyde and alkyls of α carbon atom with hydroxy in side bonds are inferred to be free radical easily to lead to oxidize coal under the ambient temperature and pressure. The order from strong to weak of oxide activation of the seven surface active groups is aldehyde side chains, hypomethylether bonds, hypoalkyl bonds of α carbon atom with hydroxyl, hypoalkyl bonds of α carbon atom with hypomethyl, hypomethyl bonds linking up two aromatic hydrocarbon,methoxy, alkyls side chains of α carbon atom with hydroxyl. Because of the two unsaturated molecular tracks of O 2, unpaired electron clouds of the part of surface active groups of coal enter molecular tracks of O 2 to lead to chemisorb on the conjugate effect and induced effect of surface active groups, and then chemical reaction followed heat happens in them. On the basis of change of bond energy, weighted average method is adopted to count the reaction heat value of each mol CO,CO 2 and H 2O. The property of coal spontaneous combustion is different for the different number and oxidability of the active structure in the coal resulting in the different oxidation heat.展开更多
A series of activated carbons（ACs） were prepared using HNO_3,H_2O_2 and steam as activation agents with the aim to introduce functional groups to carbon surface in the ACs preparation process.The effects of concentr...A series of activated carbons（ACs） were prepared using HNO_3,H_2O_2 and steam as activation agents with the aim to introduce functional groups to carbon surface in the ACs preparation process.The effects of concentration of activation agent,activation time on the surface functional groups and redox property of ACs were characterized by Temperature Program Desorption（TPD） and Cyclic Voltammetry（CV）.Results showed that lactone groups of ACs activated by HNO_3 increase with activation time,and the carboxyl groups increase with the concentration of HNO_3.Carbonyl/quinine groups of ACs activated by H_2O_2 increase with the activation time and the concentration of H_2O_2,although the acidic groups decrease with the concentration of H_2O_2.The redox property reflected by CV at 0 and 0.5 V is different with any kinds of oxygen functional groups characterized by TPD,but it is consistent with the SO_2 catalytic oxidization /oxidation properties indicated by TPR.展开更多
In order to achieve the high capacities of carbonaceous oxygen diffusion electrodes for aprotic lithiumoxygen batteries(Li-O2 batteries),most efforts currently focus on the design of rational porous architectures.Only...In order to achieve the high capacities of carbonaceous oxygen diffusion electrodes for aprotic lithiumoxygen batteries(Li-O2 batteries),most efforts currently focus on the design of rational porous architectures.Only few works study the surface chemistry effect that might be a critical factor influencing the capacities of carbonaceous electrodes.In addition,the surface chemistry effect is very difficult to be studied in composite electrodes due to the influences of binders and additives.Herein,we propose chemically activated carbon cloth(CACC) as an ideal model to investigate the effect of surface functional groups on the discharge capacities of carbonaceous oxygen electrodes for Li-O2 batteries.The intrinsic surface chemistry effect on the performance of carbonaceous cathode is directly observed for the first time without the influences of binders and additives.Results indicate that the surface carboxyl groups introduced by the chemical treatment not only function as the appropriate nucleation sites for Li2 O2 but also induce the formation of toroid-like Li2 O2.Thus,the surface carboxyl modification enhances the discharge capacities from 0.48 mAh/cm^2 of pristine carbon cloth to 1.23 mAh/cm^2 of CACC.This work presents an effective way to further optimize the carbonaceous oxygen electrodes via surface functional group engineering.展开更多
This article discussed the benzoic acid activated carbons which have changed the types and content of acid oxygen-function groups on the surface of activated carbons and their effect on the adsorption for Hg^0 in simu...This article discussed the benzoic acid activated carbons which have changed the types and content of acid oxygen-function groups on the surface of activated carbons and their effect on the adsorption for Hg^0 in simulated flue gas at 140 ℃. These surface acid oxygen function groups were identified by Boehm titration, Fourier transformation infrared spectrum, temperature programmed desorption and X-ray photoelectron spectroscopy. It indicates that the carboxyl, lactone and phenolic were formed when the benzoic acid is loaded on the surface of activated carbons. Among the surface acid oxygen function groups, the carboxyl groups enhance the adsorption capacities of Hg^0 for activated carbons to a greater extent.展开更多
In this study, the surface chemical properties of carbon nanotubes (CNTs) and carbon nanofibers (CNFs) grown by catalytic decomposition of methane on nickel and cobalt based catalysts were studied by DRIFT (Diffuse Re...In this study, the surface chemical properties of carbon nanotubes (CNTs) and carbon nanofibers (CNFs) grown by catalytic decomposition of methane on nickel and cobalt based catalysts were studied by DRIFT (Diffuse Reflectance Infrared Fourier Transform) and transmission Infrared (IR) spectroscopy. The results show that the surface exists not only carbon-hydrogen groups, but also carboxyl, ketene or quinone (carbonyl) oxygen-containing groups. These functional groups were formed in the process of the material growth, which result in large amount of chemical defect sites on the walls.展开更多
The oxyhydroxides boehmite,goethite,and manganite were synthesized,and their structure,texture,and morphology features were determined by different analytical techniques.Content of surface hydroxyl groups and zero poi...The oxyhydroxides boehmite,goethite,and manganite were synthesized,and their structure,texture,and morphology features were determined by different analytical techniques.Content of surface hydroxyl groups and zero point of charge(pH_(zpc))were measured by potentiometry,and the surface fractal dimension(D_(f))values were obtained through adsorption-desorption N_(2) iso-therms and the Pfeifer and Cole method.The synthesized materials resulted crystalline,mesoporous,pure,and thermally stable,exhibiting high surface areas,between 188 and 413 m^(2)/g.The pH_(zpc) values were 9.2,12.4,and 2.2 and surface hydroxyl group contents were for 1.16,1.7,and 0.855 meq OH-/g,for boehmite,goethite,and manganite,respectively.Surface fractal dimensions were 1.5,1.7,and 1.4 for boehmite,goethite and manganite,respectively,de-noting relatively smooth surfaces.Surface hydroxyl group content linearly correlated with D_(f) values.Characterization of these oxyhydroxides is valuable for several physicochemical adsorption processes of contaminants present in aqueous media.展开更多
Amyloid-like proteins are critical for interfacial adhesion across various marine organisms and bacteria.However,the specific contributions of different functional residues remain unclear.Herein,we introduce an approa...Amyloid-like proteins are critical for interfacial adhesion across various marine organisms and bacteria.However,the specific contributions of different functional residues remain unclear.Herein,we introduce an approach to deconstruct and mimic these residues using synthetic homopolymers and random copolymers with phenyl,amino,carboxyl,and hydroxyl functional groups using reversible addition-fragmentation chain transfer(RAFT)polymerization.The resulting polymers,designed with comparable molecular weights(M_(n):10–20 kDa)and narrow dispersities(PDI<1.3),mimic the diverse surface chemistry of amyloid-like proteins,enabling systematic investigation of their adhesive properties.The interfacial adhesion forces of different polymer films were quantified using atomic force microscopy(AFM)with a colloidal probe.Remarkably copolymers with multiple functional groups demonstrated significantly enhanced adhesion compared to homopolymers,a trend corroborated by macroscopic shear strength and stability tests.These results highlight that the synergistic effects of multiple functional groups are crucial for achieving universal interfacial adhesion of macromolecules,offering insights into protein adhesion mechanisms,and guiding polymer-based interfacial modifications.展开更多
MXenes are a novel family of two-dimensional(2D)materials that are fast gaining popularity due to their versatile characteristics.The surfaces of these materials are often functionalized by negatively charged terminal...MXenes are a novel family of two-dimensional(2D)materials that are fast gaining popularity due to their versatile characteristics.The surfaces of these materials are often functionalized by negatively charged terminal groups,such as=O,OH,and F during their synthesis,and it has been hypothesized that regulating the surface terminators enables to control the material characteristics.However,there is still a large gap between computational and experimental investigations regarding comprehending the surface functional groups.Surfaces with mixed terminations are consistently synthesized in experiments,although pure terminated surfaces are predicted by computational research.Here we summarized the nature of chemical bonding in transition metal carbide materials(MXenes)by1H and19F nuclear magnetic resonance(NMR),Raman,X-ray absorption near edge structure(XANES),extended X-ray absorption fine structure(EXAFS),ultraviolet photoelectron spectroscopy(UPS),X-ray photoelectron spectroscopy(XPS)/scanning transmission electron microscopy(STEM),and thermogravimetric analysis-mass spectrometry(TGA-MS)characterizations.Previous literature reveals that=O,–OH,–F,and–Cl are typical MXene surface terminators.However,recent comparative investigations on the valence band intensity distribution in MXenes reveal that the–OH cannot be considered an intrinsic termination species in MXenes.The surface terminals(=O,–OH,–F,and–Cl)of several MXenes,particularly V2CTxand Ti3C2Tx,will be identified and quantified here.We have also discussed different etching approaches for the synthesis of MXene,the dependence of MXene conductivity on MXene terminating groups,and the emission of various gaseous products that evolved during its chemical transformations.This paper provides significance,especially in the field of energy conversion and storage materials,where the intercalation process is crucial.展开更多
Interaction of hydrogen with TiO2 plays a vital role in TiO2-based photocatalysis and thermal catalysis. In this work, we compared thermal-, photo-, and electron-induced reactivity of various types of hydrogen species...Interaction of hydrogen with TiO2 plays a vital role in TiO2-based photocatalysis and thermal catalysis. In this work, we compared thermal-, photo-, and electron-induced reactivity of various types of hydrogen species on a rutile TiO2（110） surface formed by atomic H exposure at 320 and 115 K by means of thermal desorption spectroscopy, X-ray photoelectron spectroscopy and low energy electron diffraction. Atomic H interaction with rutile TiO2（110） at 115 K forms surface TiààH hydride, surface hydroxyl group, and chemisorbed water. Upon heating, surface TiààH hydride reacts to produce H2 while surface hydroxyl groups react to form both water and H2. Atomic H interaction with rutile TiO2（110） at 320 K strongly reduces TiO2 due to the continuous formation and desorption of water and forms surface hydroxyl groups and likely subsurface/bulk hydrogen species. Upon heating, hydrogen forms as the only gas-phase product and its desorption activation energy decreases with the subsurface/bulk reduction extent of rutile TiO2（110）. Surface Ti-H hydride exhibits photo-induced reactivity while both surface TiààH hydride and surface hydroxyl group exhibit electro-induced reactivity. These results have important implications for understanding the hydrogen-involved thermal and photo reactions on TiO2-based catalysts.展开更多
MXenes,a new family of functional two-dimensional(2 D) materials,have shown great potential for an extensive variety of applications within the last decade.Atomic defects and functional groups in MXenes are known to h...MXenes,a new family of functional two-dimensional(2 D) materials,have shown great potential for an extensive variety of applications within the last decade.Atomic defects and functional groups in MXenes are known to have a tremendous influence on the functional properties.In this review,we focus on recent progress in the characterization of atomic defects and functional group chemistry in MXenes,and how to control them to directly influence various properties(e.g.,electron transport,Li^(+) adsorption,hydrogen evolution reaction(HER) activity,and magnetism) of 2 D MXenes materials.Dynamic structural transformations such as oxidation and growth induced by atomic defects in MXenes are also discussed.The review thus provides perspectives on property optimization through atomic defect engineering,and bottom-up synthesis methods based on defect-assisted homoepitaxial growth of MXenes.展开更多
A strong influence of nitrogen gas on the content of surface hydroxyl groups of TiO2 films by atomic layer deposition（ALD） was investigated by X-ray photoelectron spectroscopy（XPS）, contact angle measuring system,...A strong influence of nitrogen gas on the content of surface hydroxyl groups of TiO2 films by atomic layer deposition（ALD） was investigated by X-ray photoelectron spectroscopy（XPS）, contact angle measuring system, and UV–Vis spectrophotometer. XPS spectra of O 1s indicate that the content of surface hydroxyl groups is varied when using N2 as carrier gas. The results of water contact angles and optical reflection spectra show that the content variation of surface hydroxyl groups influences the wetting properties and optical reflectivity of TiO2 films. A surface reaction model is suggested to explain the ALD reaction process using N2 as carrier gas.展开更多
The paper analyzed the groups naked and the transformed of fibrous brucite, wollastonite, chrysotile asbestos, sepiolite, palygorskite, clinoptilolite, crocidolite and diatomaceous earth mineral dusts by using IR unde...The paper analyzed the groups naked and the transformed of fibrous brucite, wollastonite, chrysotile asbestos, sepiolite, palygorskite, clinoptilolite, crocidolite and diatomaceous earth mineral dusts by using IR under acid and alkali etched, strong mechanical and polarized molecular interaction. The results show that the active site focuses on ends in stick dusts and on defects or hole edges in pipe dusts. The inside active sites of dusts play the main role in small molecular substance. The shape of dusts affects their distributions and densities of active sites. The strong mechanical and weak chemical force make the active site feature of minerals change, the powder process brings about more naked surface groups and more combined types. The dust activity relates to the type, contribution, and naked level of surface groups. The studied dust surface groups are mainly as follows: OH?, Mg(OH)?, Si-O-Si, Ca-O-Si, -Mg-OH2,-Al(Si)-OH, -Mg(Ca)-OH2, Ca-O,-Si???OH, Mg(Fe)-OH. Due to the difference of surface composition and structure, the minerals have a large disparity on activity and character of surface groups. The one side surface group of chrysotile layer is the same as fibrous brucite and stripped layer with more naked group. The fibrous sepiolite and palygorskite surface OH? similar to crocidolite is naked with their surface structural defects and cleavage. The more development of mineral defects, the higher of OH? (H2O+) content, the main H2O+ of clinoptilolite is partly transformed into H+, NH 4 + or OH?. The acid etched process may change OH? concentration, distribution and increase the defects and porosity of mineral fiber surface. The alkali etched has no effect on Si-O, Si-OH etc. and destroyed Al-O, Al-OH? acid site of sepiolite, palygorskite and clinoptilolite. Some surface groups of remnant differ from original dusts. The surface process of small polarized molecular or middle moleular’s branch may produce ionation and new coordinate bond, and change the active properties and level of original dusts, such as the porous minerals producing展开更多
基金FundedbytheNationalNaturalScienceFoundationofChi na (No .4 0 0 72 0 2 0 )andtheTRAPforOutstandingYoungTeachersinHigherEducationInstitutionsofMOE China
文摘The exposed and transformed groups of fibrous brucite,wollastonite,chrysotile asbestos,sepiolite,palygorskite,clinoptilolite,crocidolite and diatomaceous earth mineral materials are analyzed by IR spectra after acid and alikali etching,strong mechanical and polarity molecular interaction.The results show the active sites concentrate on the ends in stick mineral materials and on the defect or hole edge in pipe mineral materials.The inside active site of mineral materials plays a main role in small molecular substance.The shape of minerals influence their distribution and density of active site.The strong mechanical impulsion and weak chemical force change the active site feature of minerals,the powder process enables minerals exposed more surface group and more combined types.The surface processing with the small polarity molecular or the brand of middle molecular may produce ionation and new coordinate bond,and change the active properties and level of original mineral materials.
基金supported by the National Natural Science Foundation of China(51872115,52101256,and 51932003)China Postdoctoral Science Foundation Project(2020 M680043)+1 种基金Science and Technology Research Project of the Department of Education of Jilin Province(JJKH20211083KJ)2020 International Cooperation Project of the Department of Science and Technology of Jilin Province(20200801001GH).
文摘MXene quantum dots(MQDs)offer wide applications owing to the abundant surface chemistry,tunable energy-level structure,and unique properties.However,the application of MQDs in electrochemical energy conversion,including hydrogen evolution reaction(HER),remains to be realized,as it remains a challenge to precisely control the types of surface groups and tune the structure of energy levels in MQDs,owing to the high surface energy-induced strong agglomeration in post-processing.Consequently,the determination of the exact catalytically active sites and processes involved in such an electrocatalysis is challenging because of the complexity of the synthetic process and reaction conditions.Herein,we demonstrated the spontaneous evolution of the surface groups of the Ti_(2)CT_(x)MQDs(x:the content of O atom),i.e.,replacement of the-Cl functional groups by O-terminated ones during the cathode reaction.This process resulted in a low Gibbs free energy(0.26 eV)in HER.Our steady Ti_(2)CO_(x)/Cu_(2)O/Cu foam systems exhibited a low overpotential of 175 mV at 10 mA cm^(-2)in 1 M aq.KOH,and excellent operational stability over 165 h at a constant current density of-10 mA cm^(-2).
基金supported by the National Natural Science Foundation of China(Nos.12271385,12471066)the Shaanxi Fundamental Science Research Project for Mathematics and Physics(No.23JSY027)。
文摘By constructing counterexamples,the authors show that the fixed subgroups are not compressed in direct products of free and surface groups,and hence negate a conjecture in[Zhang,Q.,Ventura,E.and J.Wu,Fixed subgroups are compressed in surface groups,Internat.J.Algebra Comput.,25,2015,865–887].
基金funded by the National Natural Science Foundation of China(No.51961165104)Project of Thousand Youth Talents(No.AUGA2160100917)+1 种基金University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(No.UNPYSCT-2020050)Provincial Leading Talent Echelon Cultivation Project of Heilongjiang Institute of Technology(No.2020LJ04)。
文摘Biochar(BC)are widely used as highly efficient adsorbents to alleviate aromatics-based contaminants due to their ease of preparation,wide availability,and high sustainability.The surface properties of BCs usually vary greatly due to their complex chemical constituents and different preparation processes and are reflected in the values of parameters such as the specific surface area(SSA),pore volume/size,and surface functional groups(SFGs).The effects of SSA and pore volume/size on the adsorption of aromatics have been widely reported.However,the corresponding mechanisms of BC SFGs towards aromatics adsorption remains unclear as the compositions of the SFGs are usually complex and hard to determine.To address in this gap in the literature,this review introduces a new perspective on the adsorption mechanisms of aromatics.Through collecting previously-reported results,the parameters log P(logarithm of the Kow),polar surface area,and the positive/negative charges were carefully calculated using Chem Draw3D,which allowed the hydrophobicity/hydrophilicity properties,electron donor-acceptor interactions,Hbonding,and electrostatic interactions between SFGs and aromatics-based contaminates to be inferred intuitively.These predictions were consistent with the reported results and showed that tailor-made BCs can be designed according to the molecular weights,chemical structures,and polarities of the target aromatics.Overall,this review provides new insight into predicting the physicochemical properties of BCs through revealing the relationship between SFGs and adsorbates,which may provide useful guidance for the preparing of highly-efficient,functional BCs for the adsorption of aromatics.
文摘The activated carbon with high surface area was prepared by KOH activation.It was further modified by H2SO4 and HNO3 to introduce more surface functional groups.The pore structure of the activated carbons before and after modification was analyzed based on the nitrogen adsorption isotherms.The morphology of those activated carbons was characterized using scanning electronic microscopy （SEM）.The surface functional groups were determined by Fourier transform infrared spectroscopy （FTIR）.The quantity of those groups was measured by the Boehm titration method.Cr（VI） removal by the activated carbons from aqueous solution was investigated at different pH values.The results show that compared with H2SO4,HNO3 destructs the original pore of the activated carbon more seriously and induces more acidic surface functional groups on the activated carbon.The pH value of the solution plays a key role in the Cr（VI） removal.The ability of reducing Cr（VI） to Cr（III） by the activated carbons is relative to the acidic surface functional groups.At higher pH values,the Cr（VI） removal ratio is improved by increasing the acidic surface functional groups of the activated carbons.At lower pH values,however,the acidic surface functional groups almost have no effect on the Cr（VI） removal by the activated carbon from aqueous solution.
基金supported by the National Natural Science Foundation of China (No.52006054)the State Key Laboratory of Engines at Tianjin University (No.K2021-05)+1 种基金the European Union’s projects MODALES (No.815189)nPETS (No.954377)
文摘The thermal deactivation of diesel soot particles exerts a significant influence on the control strategy for the regeneration of diesel particulate filters(DPFs).This work focused on the changes in the surface functional groups,carbon chemical state,and graphitization degree during thermal treatment in an inert gas environment at intermediate temperatures of 600℃,800℃,and 1000℃ and explore the chemical species that were desorbed from the diesel soot surface during thermal treatment using a thermogravimetric analyser coupled with a gas-chromatograph mass spectrometer(TGA-GC/MS).The surface functional groups and carbon chemical statewere characterized using Fourier transform infrared spectroscopy(FT-IR)and X-ray photoelectron spectroscopy(XPS).The graphitization degree was evaluated by means of Raman spectroscopy(RS).The concentrations of aliphatic C–H,C–OH,C=O,and O–C=O groups are reduced for diesel soot and carbon black when increasing the thermal treatment temperature,while the sp^(2)/sp^(3) hybridized ratio and graphitization degree enhance.These results provide comprehensive evidence of the decreased reactivity of soot samples.Among oxygenated functional groups,the percentage reduction during thermal treatment is the largest for the O–C=O groups owing to its worst thermodynamic stability.TGA-GC/MS results show that the aliphatic and aromatic chains and oxygenated species would be desorbed from the soot surface during 1000℃ thermal treatment of diesel soot.
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funded by the National Natural Science Foundation of China (52100072)the Beijing Natural Science Foundation(8214056)+2 种基金the special fund of Beijing Key Laboratory of Clean Fuels and Efficient Catalytic Emission Reduction Technology,the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21021101)the National Key Research and Development Program of China (2019YFA0705803)Scientific Research Common Program of Beijing Municipal Commission of Education(KM202010017006)。
文摘FeO;supported on activated carbon(AC) has been shown to be an ideal catalyst for catalytic wet peroxide oxidation(CWPO) due to its high CWPO reaction activity and stability. Although there have been some studies on the mechanism of Fe/AC catalysis in CWPO, the specific contribution of each component(surface oxygen groups and FeOxon AC) inside an Fe/AC catalyst and their corresponding reaction mechanism remain unclear, and the reaction stability of CWPO catalysts has rarely been discussed. Then the optimal CWPO catalyst in our laboratory, 3%Fe/AC, was selected.(1) By removing certain components on the AC through heat treatment, its contribution to the reaction and the corresponding reaction mechanism were investigated. With the aid of temperature-programmed desorption–mass spectrometry(TPD–MS) and the CWPO reaction, the normalized catalytic contributions of components were shown to be: 37.3%(carboxylic groups), 5.3%(anhydride), 19.3%(ether/hydroxyl),-71.4%(carbonyl groups) and 100%(FeOx),respectively. DFT calculation and EPR analysis confirmed that carboxylic groups and Fe_(2)O_(3) are able to activate the H_(2)O_(2) to generate·OH.(2) The catalysts at were characterized at different reaction times(0 h, 450 h, 900 h, 1350 h, and 1800 h) by TPD–MS and M?ssbauer spectroscopy. Results suggested that the number of carboxylic goups gradually increased and the size of paramagnetic Fe_(2)O_(3) particle crystallites gradually increased as the reactions progressed. The occurrence of strong interactions between metal oxides and AC was also confirmed. Due to these effects, the strong stability of 3%Fe/AC was further improved. Therefore, the reasons for the high activity and strong stability of 3%Fe/AC in CWPO were clearly shown. We believe that this work provides an idea of the removal of cresols from wastewater into the introduction to show the potential applications of CWPO.
文摘The oxidation heat of coal is the direct reason leading to coal spontaneous combustion. When coal is exposed in oxygen atmosphere, the physical adsorption and chemisorption happened, and then which resulting chemical reaction followed heat between coal and oxygen. Owing to the complexity and uncertain of molecular structure of coal,it was only reduced that bridge bonds, side chains and O 2 containing functional groups in coal may be prone to oxidation in last year, but not to deeply investigate into the structures and the type of the active radicals. In this paper, according to the last achievements in coal structure research, the hypomethylether bond, hypoalkyl bond of α carbon atom with hydroxyl and α carbon atom with hypomethy side chain and hypomethyl bonds linking up two aromatic hydrocarbon in bridge bonds, and methoxy,aldehyde and alkyls of α carbon atom with hydroxy in side bonds are inferred to be free radical easily to lead to oxidize coal under the ambient temperature and pressure. The order from strong to weak of oxide activation of the seven surface active groups is aldehyde side chains, hypomethylether bonds, hypoalkyl bonds of α carbon atom with hydroxyl, hypoalkyl bonds of α carbon atom with hypomethyl, hypomethyl bonds linking up two aromatic hydrocarbon,methoxy, alkyls side chains of α carbon atom with hydroxyl. Because of the two unsaturated molecular tracks of O 2, unpaired electron clouds of the part of surface active groups of coal enter molecular tracks of O 2 to lead to chemisorb on the conjugate effect and induced effect of surface active groups, and then chemical reaction followed heat happens in them. On the basis of change of bond energy, weighted average method is adopted to count the reaction heat value of each mol CO,CO 2 and H 2O. The property of coal spontaneous combustion is different for the different number and oxidability of the active structure in the coal resulting in the different oxidation heat.
基金part of the Innovation Program for Undergraduate supported by China University of Mining & Technology,Beijing.
文摘A series of activated carbons（ACs） were prepared using HNO_3,H_2O_2 and steam as activation agents with the aim to introduce functional groups to carbon surface in the ACs preparation process.The effects of concentration of activation agent,activation time on the surface functional groups and redox property of ACs were characterized by Temperature Program Desorption（TPD） and Cyclic Voltammetry（CV）.Results showed that lactone groups of ACs activated by HNO_3 increase with activation time,and the carboxyl groups increase with the concentration of HNO_3.Carbonyl/quinine groups of ACs activated by H_2O_2 increase with the activation time and the concentration of H_2O_2,although the acidic groups decrease with the concentration of H_2O_2.The redox property reflected by CV at 0 and 0.5 V is different with any kinds of oxygen functional groups characterized by TPD,but it is consistent with the SO_2 catalytic oxidization /oxidation properties indicated by TPR.
基金supported by grants from the National Natural Science Foundation of China (Nos.21673169,51672205)the National Key R&D Program of China (No.2016YFA0202602)+1 种基金the Research Start-Up Fund from Wuhan University of Technologythe Fundamental Research Funds for the Central Universities (WUT:Nos.2019IB003,2016IVA083)
文摘In order to achieve the high capacities of carbonaceous oxygen diffusion electrodes for aprotic lithiumoxygen batteries(Li-O2 batteries),most efforts currently focus on the design of rational porous architectures.Only few works study the surface chemistry effect that might be a critical factor influencing the capacities of carbonaceous electrodes.In addition,the surface chemistry effect is very difficult to be studied in composite electrodes due to the influences of binders and additives.Herein,we propose chemically activated carbon cloth(CACC) as an ideal model to investigate the effect of surface functional groups on the discharge capacities of carbonaceous oxygen electrodes for Li-O2 batteries.The intrinsic surface chemistry effect on the performance of carbonaceous cathode is directly observed for the first time without the influences of binders and additives.Results indicate that the surface carboxyl groups introduced by the chemical treatment not only function as the appropriate nucleation sites for Li2 O2 but also induce the formation of toroid-like Li2 O2.Thus,the surface carboxyl modification enhances the discharge capacities from 0.48 mAh/cm^2 of pristine carbon cloth to 1.23 mAh/cm^2 of CACC.This work presents an effective way to further optimize the carbonaceous oxygen electrodes via surface functional group engineering.
文摘This article discussed the benzoic acid activated carbons which have changed the types and content of acid oxygen-function groups on the surface of activated carbons and their effect on the adsorption for Hg^0 in simulated flue gas at 140 ℃. These surface acid oxygen function groups were identified by Boehm titration, Fourier transformation infrared spectrum, temperature programmed desorption and X-ray photoelectron spectroscopy. It indicates that the carboxyl, lactone and phenolic were formed when the benzoic acid is loaded on the surface of activated carbons. Among the surface acid oxygen function groups, the carboxyl groups enhance the adsorption capacities of Hg^0 for activated carbons to a greater extent.
文摘In this study, the surface chemical properties of carbon nanotubes (CNTs) and carbon nanofibers (CNFs) grown by catalytic decomposition of methane on nickel and cobalt based catalysts were studied by DRIFT (Diffuse Reflectance Infrared Fourier Transform) and transmission Infrared (IR) spectroscopy. The results show that the surface exists not only carbon-hydrogen groups, but also carboxyl, ketene or quinone (carbonyl) oxygen-containing groups. These functional groups were formed in the process of the material growth, which result in large amount of chemical defect sites on the walls.
文摘The oxyhydroxides boehmite,goethite,and manganite were synthesized,and their structure,texture,and morphology features were determined by different analytical techniques.Content of surface hydroxyl groups and zero point of charge(pH_(zpc))were measured by potentiometry,and the surface fractal dimension(D_(f))values were obtained through adsorption-desorption N_(2) iso-therms and the Pfeifer and Cole method.The synthesized materials resulted crystalline,mesoporous,pure,and thermally stable,exhibiting high surface areas,between 188 and 413 m^(2)/g.The pH_(zpc) values were 9.2,12.4,and 2.2 and surface hydroxyl group contents were for 1.16,1.7,and 0.855 meq OH-/g,for boehmite,goethite,and manganite,respectively.Surface fractal dimensions were 1.5,1.7,and 1.4 for boehmite,goethite and manganite,respectively,de-noting relatively smooth surfaces.Surface hydroxyl group content linearly correlated with D_(f) values.Characterization of these oxyhydroxides is valuable for several physicochemical adsorption processes of contaminants present in aqueous media.
基金supported by the National Natural Science Foundation of China(Nos.22375122 and 22105065)the National Science Fund for Distinguished Young Scholars(No.52225301)+3 种基金the National Key R&D Program of China(Nos.2020YFA0710400 and 2020YFA0710402)the 111 Project(No.B14041)Fundamental Research Funds for Central Universities(No.GK202304040)Open Project of the State Key Laboratory of Supramolecular Structure and Materials(No.sklssm2024023)。
文摘Amyloid-like proteins are critical for interfacial adhesion across various marine organisms and bacteria.However,the specific contributions of different functional residues remain unclear.Herein,we introduce an approach to deconstruct and mimic these residues using synthetic homopolymers and random copolymers with phenyl,amino,carboxyl,and hydroxyl functional groups using reversible addition-fragmentation chain transfer(RAFT)polymerization.The resulting polymers,designed with comparable molecular weights(M_(n):10–20 kDa)and narrow dispersities(PDI<1.3),mimic the diverse surface chemistry of amyloid-like proteins,enabling systematic investigation of their adhesive properties.The interfacial adhesion forces of different polymer films were quantified using atomic force microscopy(AFM)with a colloidal probe.Remarkably copolymers with multiple functional groups demonstrated significantly enhanced adhesion compared to homopolymers,a trend corroborated by macroscopic shear strength and stability tests.These results highlight that the synergistic effects of multiple functional groups are crucial for achieving universal interfacial adhesion of macromolecules,offering insights into protein adhesion mechanisms,and guiding polymer-based interfacial modifications.
基金supported by the National Natural Science Foundation of China(21703147 and U1401248)the support of China Scholarship Council(2018SLJ022487)。
文摘MXenes are a novel family of two-dimensional(2D)materials that are fast gaining popularity due to their versatile characteristics.The surfaces of these materials are often functionalized by negatively charged terminal groups,such as=O,OH,and F during their synthesis,and it has been hypothesized that regulating the surface terminators enables to control the material characteristics.However,there is still a large gap between computational and experimental investigations regarding comprehending the surface functional groups.Surfaces with mixed terminations are consistently synthesized in experiments,although pure terminated surfaces are predicted by computational research.Here we summarized the nature of chemical bonding in transition metal carbide materials(MXenes)by1H and19F nuclear magnetic resonance(NMR),Raman,X-ray absorption near edge structure(XANES),extended X-ray absorption fine structure(EXAFS),ultraviolet photoelectron spectroscopy(UPS),X-ray photoelectron spectroscopy(XPS)/scanning transmission electron microscopy(STEM),and thermogravimetric analysis-mass spectrometry(TGA-MS)characterizations.Previous literature reveals that=O,–OH,–F,and–Cl are typical MXene surface terminators.However,recent comparative investigations on the valence band intensity distribution in MXenes reveal that the–OH cannot be considered an intrinsic termination species in MXenes.The surface terminals(=O,–OH,–F,and–Cl)of several MXenes,particularly V2CTxand Ti3C2Tx,will be identified and quantified here.We have also discussed different etching approaches for the synthesis of MXene,the dependence of MXene conductivity on MXene terminating groups,and the emission of various gaseous products that evolved during its chemical transformations.This paper provides significance,especially in the field of energy conversion and storage materials,where the intercalation process is crucial.
基金financially supported by the National Natural Science Foundation of China (Nos. 21525313, 21761132005)Chinese Academy of Sciences (No. KJZD-EW-M03)+1 种基金MOE Fundamental Research Funds for the Central Universities (No. WK2060030017)Collaborative Innovation Center of Suzhou Nano Science and Technology
文摘Interaction of hydrogen with TiO2 plays a vital role in TiO2-based photocatalysis and thermal catalysis. In this work, we compared thermal-, photo-, and electron-induced reactivity of various types of hydrogen species on a rutile TiO2（110） surface formed by atomic H exposure at 320 and 115 K by means of thermal desorption spectroscopy, X-ray photoelectron spectroscopy and low energy electron diffraction. Atomic H interaction with rutile TiO2（110） at 115 K forms surface TiààH hydride, surface hydroxyl group, and chemisorbed water. Upon heating, surface TiààH hydride reacts to produce H2 while surface hydroxyl groups react to form both water and H2. Atomic H interaction with rutile TiO2（110） at 320 K strongly reduces TiO2 due to the continuous formation and desorption of water and forms surface hydroxyl groups and likely subsurface/bulk hydrogen species. Upon heating, hydrogen forms as the only gas-phase product and its desorption activation energy decreases with the subsurface/bulk reduction extent of rutile TiO2（110）. Surface Ti-H hydride exhibits photo-induced reactivity while both surface TiààH hydride and surface hydroxyl group exhibit electro-induced reactivity. These results have important implications for understanding the hydrogen-involved thermal and photo reactions on TiO2-based catalysts.
基金supported by the National Natural Science Foundation of China(No.51902237)the Fundamental Research Funds for the Central Universities of China(No.WUT:2019III012GX)+1 种基金Nanostructure Research Center(NRC),and Center for Materials Analysis and Testing at Wuhan University of TechnologyA portion of this work was supported by the Fluid Interface Reactions,Structures and Transport(FIRST)Center,an Energy Frontier Research Center funded by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences(RRU)。
文摘MXenes,a new family of functional two-dimensional(2 D) materials,have shown great potential for an extensive variety of applications within the last decade.Atomic defects and functional groups in MXenes are known to have a tremendous influence on the functional properties.In this review,we focus on recent progress in the characterization of atomic defects and functional group chemistry in MXenes,and how to control them to directly influence various properties(e.g.,electron transport,Li^(+) adsorption,hydrogen evolution reaction(HER) activity,and magnetism) of 2 D MXenes materials.Dynamic structural transformations such as oxidation and growth induced by atomic defects in MXenes are also discussed.The review thus provides perspectives on property optimization through atomic defect engineering,and bottom-up synthesis methods based on defect-assisted homoepitaxial growth of MXenes.
基金financially supported by the National Science and Technology Major Project (No. 2009ZX02037-003)the China Postdoctoral Science Foundation (No. 2011M500996)
文摘A strong influence of nitrogen gas on the content of surface hydroxyl groups of TiO2 films by atomic layer deposition（ALD） was investigated by X-ray photoelectron spectroscopy（XPS）, contact angle measuring system, and UV–Vis spectrophotometer. XPS spectra of O 1s indicate that the content of surface hydroxyl groups is varied when using N2 as carrier gas. The results of water contact angles and optical reflection spectra show that the content variation of surface hydroxyl groups influences the wetting properties and optical reflectivity of TiO2 films. A surface reaction model is suggested to explain the ALD reaction process using N2 as carrier gas.
文摘The paper analyzed the groups naked and the transformed of fibrous brucite, wollastonite, chrysotile asbestos, sepiolite, palygorskite, clinoptilolite, crocidolite and diatomaceous earth mineral dusts by using IR under acid and alkali etched, strong mechanical and polarized molecular interaction. The results show that the active site focuses on ends in stick dusts and on defects or hole edges in pipe dusts. The inside active sites of dusts play the main role in small molecular substance. The shape of dusts affects their distributions and densities of active sites. The strong mechanical and weak chemical force make the active site feature of minerals change, the powder process brings about more naked surface groups and more combined types. The dust activity relates to the type, contribution, and naked level of surface groups. The studied dust surface groups are mainly as follows: OH?, Mg(OH)?, Si-O-Si, Ca-O-Si, -Mg-OH2,-Al(Si)-OH, -Mg(Ca)-OH2, Ca-O,-Si???OH, Mg(Fe)-OH. Due to the difference of surface composition and structure, the minerals have a large disparity on activity and character of surface groups. The one side surface group of chrysotile layer is the same as fibrous brucite and stripped layer with more naked group. The fibrous sepiolite and palygorskite surface OH? similar to crocidolite is naked with their surface structural defects and cleavage. The more development of mineral defects, the higher of OH? (H2O+) content, the main H2O+ of clinoptilolite is partly transformed into H+, NH 4 + or OH?. The acid etched process may change OH? concentration, distribution and increase the defects and porosity of mineral fiber surface. The alkali etched has no effect on Si-O, Si-OH etc. and destroyed Al-O, Al-OH? acid site of sepiolite, palygorskite and clinoptilolite. Some surface groups of remnant differ from original dusts. The surface process of small polarized molecular or middle moleular’s branch may produce ionation and new coordinate bond, and change the active properties and level of original dusts, such as the porous minerals producing
