三聚氰酸在活性炭纤维毡表面的吸附及电脱附行为的研究

利用活性炭纤维毡(ACF)对三聚氰酸进行了静态吸附和电脱附,通过透射电子显微镜(TEM)、场发射扫描电子显微镜(SEM)对ACF微观结构进行了表征,并通过高效液相色谱(HPLC)检测了三聚氰酸含量.研究了吸附平衡时间、pH等对静态吸附的影响,以及电解质浓度和脱附时间对电脱附率的影响.结果表明:ACF对三聚氰酸的吸附遵循准二级吸附动力学,符合Langmuir和Freundlich等温吸附模型,酸性环境能促进对三聚氰酸的吸附,pH=12时发生脱附再生,用ACF电脱附三聚氰酸最佳脱附时间15min时脱附率可达92.5%.

挥发性有机物在活性炭纤维上的吸附和电致热脱附

采用3种不同的活性炭纤维,考察了VOCs种类、VOCs浓度以及床层温度对活性炭纤维吸附VOCs性能的影响,并采用电致热脱附技术进行再生研究.结果表明,甲苯浓度对吸附推动力影响较大,在高浓度下,可使吸附容量达到434.8mg/g.活性炭纤维吸附甲苯受温度影响较小,在60℃下仍然具有288.6mg/g的吸附容量.电致热脱附电压越大,活性炭纤维升温速率越快,脱附效率越高,经过100min即可完全脱附.经过4次吸脱附循环,活性炭纤维仍有较好的吸附效果,饱和吸附量能达到原有吸附量的80%以上.

载钛活性炭电吸附去除Cr(Ⅵ)的研究

采用sol-gel法制备了载钛活性炭,并用于电吸附处理含铬废水。当Cr(Ⅵ)初始浓度为20 mg/L时,载钛活性炭上施加1.2 V的正向电压,电吸附3 h后的处理水水质满足国家排放标准。研究了载钛活性炭电吸附去除Cr(Ⅵ)的影响因素及TiAC的电脱附再生。

介孔碳吸附再生组合工艺处理难降解有机磷废水

以自制介孔碳(MC)为吸附剂,采用吸附—电-臭氧-UV再生组合工艺将难降解有机磷三(2-羧乙基)膦(TCEP)富集后转化为磷酸盐释放,为后续磷回收提供基础。运用TEM,SEM,XRD等技术对MC进行了表征。表征结果显示,MC为碳纳米线堆积有序介孔结构,比表面积为699.76 m2/g,可为有机磷提供吸附位点。在吸附温度为298 K、TCEP初始质量浓度为100 mg/L、吸附剂投加量为1 g/L的条件下,MC对TCEP的平衡吸附量为33.72 mg/g。利用电-臭氧-UV对MC进行再生,总磷释放率可达100%,并基本矿化为磷酸盐,再生效率显著高于臭氧、臭氧-H2O2、臭氧-UV等方法。

Femtosecond Two-Photon Detachment of Cu^- Studied By Photoelectron Imaging

The wavelength dependence of photoelectron angular distributions （PADs） of two-photon detachment of Cu^- has been directly studied by using the photoelectron map imaging. Results show that for the laser field intensity of 6.0×10^10W/cm^2, PADs exhibit dramatic change with the external field wavelength. Comparison between the experimental observation and the lowest-order perturbation theory prediction indicates that the pattern of PADs can be explained by the interference of the s and d partial waves in the final state. Relative contri- butions of s and d partial waves in the two-photon detachment at different laser wavelengths are obtained.

Determination of the Real Surface Area of Palladium Electrode

Four methods, including voltammetric measurement of double layer capacitance, surface oxides reduction, under potential deposition of Cu and carbon monoxide （CO） stripping have been applied to evaluate the real surface area of a polycrystalline Pd （pc-Pd） electrode. The results reveal that the second and third methods lead to consistent results with deviations below 5%. And from the determined double layer capacitance and CO stripping charge, it is deduced that the double layer capacity unit area is 23.1±0.4μF/cm2 and the saturated CO adlayer should be ca. 0.66 ML in order to ensure that the real surface area as determined is consistent with the other two techniques. The applicability as well as the attentions when applying these techniques for the determination of the real surface area of pc-Pd electrodes have been discussed.

Unravelling Hydrogen Adsorption Kinetics on Ir(111)Electrode in Acid Solutions by Impedance Spectroscopy

The kinetics for hydrogen(H)adsorption on Ir(111)electrode has been studied in both HClO_(4) and H_(2)SO_(4) solutions by impedance spectroscopy.In HClO_(4),the adsorption rate for H adsorption on Ir(111)increases from 1.74×10^(-8)mol·cm^(-2)·s^(-1) to 3.47×10^(-7)mol·cm^(-2)·s^(-1) with the decrease of the applied potential from 0.2 V to 0.1 V(vs.RHE),which is ca.one to two orders of magnitude slower than that on Pt(111)under otherwise identical condition.This is explained by the stronger binding of water to Ir(111),which needs a higher barrier to reorient during the under potential deposition of H from hydronium within the hydrogen bonded water network.In H_(2)SO_(4),the adsorption potential is ca.200 mV negatively shifted,accompanied by a decrease of adsorption rate by up to one order of magnitude,which is explained by the hindrance of the strongly adsorbed sulfate/bisulfate on Ir(111).Our results demonstrate that under electrochemical environment,H adsorption is strongly affected by the accompanying displacement and reorientation of water molecules that initially stay close to the electrode surface.

Synthesis and electrochemical behavior of monolayer-Ti_(3)C_(2)T_(x) for capacitive deionization

MXene materials have got great attention from researchers of environmental treatment for the great electrochemical performance.Monolayer-Ti_(3)C_(2)T_(x)(T_(x) is the surface terminal groups such as-O,-OH and/or-F species),as a typical structural MXene,always shows better chemical-physical characteristics than multilayer-Ti_(3)C_(2)T_(x).Thus,we prepared monolayer-Ti_(3)C_(2)T_(x) electrode by HF etching method and absolute ethyl alcohol intercalationdelamination treatment for capacitive deionization(CDI).The prepared monolay-Ti_(3)C_(2)T_(x) shows a higher specific surface area(235.6 m^(2)/g)and a thinner thickness(0.8 nm).Moreover,a series of systematic investigation demonstrated that monolayer-Ti_(3)C_(2)T_(x) has obvious promotional phenomenon on electrochemical properties(e.g.,mass specific capacitance increased from 52.1 F/g to 144.7 F/g).The NaCl adsorption capacity of monolayer-Ti_(3)C_(2)T_(x),is 30.7 mg/g in 1000 mg/L NaCl solution at 1.2 V.We concluded that the electro-sorption mechanism could be expressed as double electric layer and monolayer coverage by a good fitting of Langmuir isotherms and the pseudo-second-order kinetics equation.This work would provide a new strategy for the application of monolayer-Ti_(3)C_(2)T_(x) material in wastewater treatment in the future.

Palladium-copper nanodot as novel H_(2)-evolution cocatalyst:Optimizing interfacial hydrogen desorption for highly efficient photocatalytic activity

Noble metal palladium(Pd)is well‐known as excellent photocatalytic cocatalyst,but its strong adsorption to hydrogen causes its limited H2‐evolution activity.In this study,the transition metal Cu was successfully introduced into the metallic Pd to weaken its hydrogen‐adsorption strength to improve its interfacial H_(2)‐evolution rate via the Pd‐Cu alloying effect.Herein,the ultrasmall Pd_(100−x)Cu_(x) alloy nanodots(2−5 nm)as a novel H_(2)‐evolution cocatalyst were integrated with the TiO_(2) through a simple NaH_(2)PO_(2)‐mediated co‐deposition route.The resulting Pd_(100−x)Cu_(x)/TiO_(2) sample shows the significantly enhanced photocatalytic H_(2)‐generation performance(269.2μmol h^(−1)),which is much higher than the bare TiO2.Based on in situ irradiated X‐ray photoelectron spectroscopy(ISI‐XPS)and density functional theory(DFT)results,the as‐formed Pd_(100−x)Cu_(x) alloy nanodots can effectively promote the separation of photo‐generated charges and weak the adsorption strength for hydrogen to optimize the process of hydrogen‐desorption process on Pd_(75)Cu_(25) alloy,thus leading to high photocatalytic H_(2)‐evolution activity.Herein,the weakened H adsorption of Pd_(75)Cu_(25) cocatalyst can be ascribed to the formation of electron‐rich Pd after the introduction of weak electronegativity Cu.The present work about optimizing electronic structure for promoting interfacial reaction activity provides a new sight for the development of the highly efficient photocatalysts.

Aromatization of Methanol over La/Zn/HZSM-5 Catalysts

Aromatization of methanol over co-impregnated La/Zn/HZSM-5 zeolite catalyst was studied.The selectivity of aromatics and BTX(benzene,toluene,and xylene)reached 64.0%and 56.6%,respectively,using La/Zn/HZSM-5 at 437°C,0.1 MPa and methanol WHSV(weight hourly space velocity)=0.8 h-1.Catalytic results showed that the La species was a very good promoter,increased selectivity of aromatics,and prolonged the catalyst lifetime on stream.The effects of the SiO2/Al2O3 ratio in zeolite,Zn and La loading,WHSV,reaction temperature, water content in the feed and H2 pretreatment of catalysts on the catalytic performance were studied in detail. Characterizations of the catalysts by thermogravimetric analysis(TGA),NH3-TPD(temperature programmed desorption),SEM(scanning electron micrograph),N2 adsorption-desorption,XRD(X-ray diffraction)and XRF (X-ray fluorescence),were carried out to understand the structure and discuss the aromatization performance of La/Zn/HZSM-5 zeolite catalyst.

Catalytic Performance of Graphite Oxide Supported Au Nanoparticles in Aerobic Oxidation of Benzyl Alcohol： Support Effect

Various Au/GO catalysts were prepared by depositing Au nanoparticles on thermally- and chemically-treated graphite oxide （GO） supports using a sol-immobilization method. The surface chemistry and structure of GO supports were characterized by a series of analytical techniques including X-ray photoelectron spectroscopy, temperature-programmed desorption and Raman spectroscopy. The results show that thermal and chemical treatments have large influence on the presence of surface oxygenated groups and the crystalline structure of GO supports. A strong support effect was observed on the catalytic activity of Au/GO catalysts in the liquid phase aerobic oxidation of benzyl alcohol. Compared to the amount and the type of surface oxygen functional groups, the ordered structure of GO supports may play a more important role in determining the catalytic performance of Au/GO catalysts.

Photochemistry of Potassium Ferrocyanide and its Reaction with Uridine 5′-monophosphate in Aqueous Solution under Ultraviolet Irradiation

The photochemical reaction of potassium ferrocyanide(K_(4)Fe(CN)_(6))exhibits excitation wavelength dependence and non-Kasha rule behavior.In this study,the excited-state dynamics of K_(4)Fe(CN)_(6) were studied by transient absorption spectroscopy.Excited state electron detachment(ESED)and photoaquation reactions were clarified by comparing the results of 260,320,340,and 350 nm excitations.ESED is the path to generate a hydrated electron(e^(−)_(aq)).ESED energy barrier varies with the excited state,and it occurs even at the first singlet excited state(^(1)T_(1g)).The ^(1)T_(1g) state shows∼0.2 ps lifetime and converts into triplet[Fe(CN)_(6)]4−by intersystem crossing.Subsequently,3Fe(CN)_(5)]^(3-)appears after one CN−ligand is ejected.In sequence,H2O attacksFe(CN)_(5)]^(3-)to generate[Fe(CN)_(5)H_(2)O]^(3−)with a time constant of approximately 20 ps.The ^(1)T_(1g) state and e−aq exhibit strong reducing power.The addition of uridine 5′-monophosphate(UMP)to the K_(4)Fe(CN)_(6) solution decrease the yield of e−aq and reduce the lifetimes of the e−aq and ^(1)T_(1g) state.The obtained reaction rate constant of ^(1)T_(1g) state and UMP is 1.7×10^(14)(mol/L)^(−1)·s^(−1),and the e−aq attachment to UMP is∼8×10^(9)(mol/L)^(−1)·s^(−1).Our results indicate that the reductive damage of K_(4)Fe(CN)_(6) solution to nucleic acids under ultraviolet irradiation cannot be neglected.

Characterization of Catalytic Cracking Catalysts Regenerated by Gasifying Deposited Coke

Partially or fully regenerated catalytic cracking catalysts were prepared by gasifying the coke deposited on coked catalysts with a gaseous mixture of oxygen and steam in a fixed fluidized bed （FFB）. The resultant samples were characterized by different methods such as the nitrogen adsorption-desorption analysis, the X-ray diffractometry, the infrared spectroscopy, the ammonia temperature-programmed desorption （NH3-TPD） method, the X-ray fluorescence （XRF） analysis, the transmission electron microscopy and energy dispersive X-ray spectroscopy （TEM-EDX）, the thermal-gravimetric analysis （TGA） and the differential thermal analysis （DTA）. The results showed that exposure of catalyst to steam for about 10 minutes at temperature ≥ 800 ℃ could not cause too much destruction of the catalysts, and an amount of coke equating to about 0.27 m% was enough to block approximately all acid sites in micro-pores of the zeolite catalyst. Coke didn＇t show equal reactivity during coke burning-off that could be accelerated by the catalytic action of nearby metal atoms. However, when the carbon content on the catalyst reached about 2.44 m%, the catalytic action of metals on the catalyst was not evident. The severe thermal and hydrothermal environment during exposure of the catalyst to steam at a temperature in the range of about 860--880 ℃ for 30 minutes could lead to collapse of pore structure and transformation of crystal phase and consequently decrease of the surface area and acid amount on the catalyst.

Oxidation of Mercaptans from Light Oil Sweetening by Fe_2O_3/MgO/Al_2O_3 Supported CoPcS Catalyst

MgO/Al2O3 and Fe2O3/MgO/Al2O3 solid bases were prepared through mixing method. After sulfonated cobalt phthalocyanine （CoPcS） being supported on these solid bases, the catalytic performance of these catalysts was evaluated by means of mercaptan oxidation reaction. The samples were characterized by X-ray diffraction （XRD）, CO2 temperature-programmed desorption （CO2-TPD）, FTIR spectroscopy, and X-ray photoelectron spectroscopy （XPS）. Investigation was focused on the effect of Fe2O3 on activity, crystal structure, basicity, and stability of the catalyst and also on the role of Fe2O3 in the mercaptan oxidation processes. Test results have shown that the Fe2O3/MgO/Al2O3- CoPcS catalyst has a higher initial activity and a much longer service life than the MgO/Al2O3-CoPcS catalyst. The increased types of basic sites coupled with an enhanced oxidation ability resulted from the addition of Fe2O3 have contributed to the improvement of the catalytic activity of the MgO/Al2O3-CoPcS catalyst.

Novel synthesis of nickel oxide microsphere with high surface area and its catalytic application for carbon dioxide reforming of methane

Nickel oxide(NiO)microsphere with a large surface area was novelly synthesized through nickel bicarbonate(Ni(HCO3)2)precursor.The obtained nickel oxide(NiO)microsphere was characterized by X-ray pattern diffraction,scanning electron microscopy,CO2 temperature-programmed desorption,H2 temperature-programmed reduction,N2 adsorption/desorption and laser scattering particle size distribution analyzer.It was found that nickel oxide(NiO)synthesized by the thermal decomposition of Ni(HCO3)2through area hydrolysis,presented very nice microsphere with high surface area.The catalytic properties of obtained nickel oxide(NiO)microsphere were studied in the reaction of carbon dioxide reforming of methane where 91.3% conversion of CH4 with 93% conversion of CO2 was observed.Besides,the catalyst maintained high stability over 200 h on the stream.

Preparation and Visible-Light Photocatalytic Activity of FeTPP-Cr-TiO2 Microspheres

Tetraphenyl-porphyrin iron （FeTPP） was chosen to sensitize Cr doped TiO2 （Cr-TiO2） nanoparticles, a novel multimodified photocatalyst FeTPP-Cr-TiO2 with excellent visible- light photocatalytic activity was successfully synthesized. The FeTPP-Cr-TiO2 microspheres were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electronic microscopy, X-ray photoelectron spectroscopy, UV-Vis diffuse reflectance spectra and N2 adsorption-desorption isotherms. The photocatalytic activity of FeTPP-Cr-TiO2 was evaluated by degradations of methylene blue in aqueous solution under irradiation with Xe lamp （150 W）. The results showed that the FeTPP-Cr-TiO2 multimodified photocatalyst was anatase phase with high specific surface area （74.7 m^2/g）, and exhibited higher photocatalytic degradation efficiency than Cr-TiO2 and FeTPP-TiO2. The photocatalytic degradations of three quinolone antibiotics （lomefioxacin, norfioxacin, and ofioxacin） were further estimated for the feasibility of practical application of catalyst in wastewater treatment. It is desirable that photodegradation of antibiotics with FeTPP-Cr-TiO2 achieved pretty high degradation rates and all followed the pseudo first-order reaction model, and the rate constants k of 3.02×10^-2, 2.81×10^-2, and 3.86×10^-2 min-1 and the half-lifes t1/2 of 22.9, 24.6, and 17.9 min were achieved respectively.

Solid superacid-catalyzed hydroconversion of an extraction residue from Lingwu bituminous coal

A solid superacid was prepared as a catalyst. The catalyst was characterized by ammonia temperature- programmed desorption, surface property measurement, and analyses with scanning electron micros- copy and Fourier transform infrared spectrometry. A extraction residue from Lingwu subbituminous coal was subject to non-catalytic and catalytic hydroconversion using cyclohexane as the solvent under pres- surized hydrogen at 300 ℃ for 3 h. The results show that the total yield of petroleum ether-extractable arenes from catalytic hydroconversion is much higher than that from non-catalytic hydroconversion. The cleavage of Car-Cask bonds in the residue could significantly proceed during catalytic hvdrncnnvarsion

Vapour Phase Alkylation of Naphthalene over Lanthana Modified Zeolites

Lanthanum oxide impregnated large-pore zeolite catalysts were prepared. The catalysts were characterized by XRD （X-ray diffraction）, PSA （particle size analysis）, TPD （temperature programmed desorption） and SEM （scanning electron microscope）. The performances of the catalysts were investigated using the alkylation reaction of naphthalene with methanol. Under comparable conditions, the La-impregnated β-zeolite catalyst showed the highest catalytic activity among all the catalysts tested. The lower reaction temperature is favorable for the formation of 2,6-dimethyl naphthalene.

Effect of Fe/Al Hydroxides on Desorption of K^+ and NH_4^+ from Two Soils and Kaolinite

Potassium （K） and nitrogen （N） are essential nutrients for plants. Adsorption and desorption in soils affect K＋ and NH4＋ avail- abilities to plants and can be affected by the interaction between the electrical double layers on oppositely charged particles because the interaction can decrease the surface charge density of the particles by neutralization of positive and negative charges. We studied the effect of iron （Fe）/aluminum （Al） hydroxides on desorption of K＋ and NH4＋ from soils and kaolinite and proposed desorption mechanisms based on the overlapping of diffuse layers between negatively charged soils and mineral particles and the positively charged Fe/Al hydroxide particles. Our results indicated that the overlapping of diffuse layers of electricM double layers between positively charged Fe/Al hydroxides, as amorphous Al（OH）3 or Fe（OH）3, and negatively charged surfaces from an Ultisol, an Alfisol, and a kaolinite standard caused the effective negative surface charge density on the soils and kaolinite to become less negative. Thus the adsorption affinity of these negatively charged surfaces for K＋ and NH4＋ declined as a result of the incorporation of the Fe/Al hydroxi- des. Consequently, the release of exchangeable K＋ and NH4＋ from the surfaces of the soils and kaolinite increased with the amount of the Fe/A1 hydroxides added. The greater the positive charge on the surfaces of Fe/Al hydroxides, the stronger was the interactive effect between the hydroxides and soils or kaolinite, and thus the more release of K＋ and NH4＋. A decrease in pH led to increased positive surface charge on the Fe/Al hydroxides and enhanced interactive effects between the hydroxides and soils/kaolinite. As a result, more K＋ and NH4＋ were desorbed from the soils and kaolinite. This study suggests that the interaction between oppositely charged particles of variable charge soils can enhance the mobility of K＋ and NH4＋ in the soils and thus increase their leaching loss.