Achieving high-efficient photocatalytic persulfate-activated degradation of tetracycline via carbon dots modified MIL-101(Fe)octahedrons

The synergistic reaction of photocatalysis and advanced oxidation is a valid strategy for the degradation of harmful antibiotic wastewater.Herein,carbon dots(CDs)modified MIL-101(Fe)octahedrons to form CDs/MIL-101(Fe)composite photocatalyst was synthesized for visible light-driven photocatalytic/persulfate(PS)-activated tetracycline(TC)degradation.The electron spin resonance(ESR)spectra,scavenging experiment and electrochemical analysis were carried out to reveal that the high visible light-driven photocatalytic degradation activity of TC over CDs/MIL-101(Fe)photocatalysts is not only ascribed to the production of free active radicals in the CDs/MIL-101(Fe)/PS system(·OH,·SO_(4-),^(1)O_(2),h^(+)and·O_(2)^(-))but also attributed to the consumption of electrons caused by the PS,which can suppress the recombination of photo-generated carriers as well as strong light scattering and electron trapping effects of CDs.Finally,the possible degradation pathways were proposed by analyzing intermediates via liquid chromatography-mass spectrometry technique.This research presents a rational design conception to construct a CDs/PS-based photocatalysis/advanced oxidation technology with high-efficient degradation activity for the remediation of organic antibiotic pollutant wastewater and for the improvement of carrier transport kinetics of photocatalysts.

Elimination, Kinetics and Thermodynamics of Fe(II) Ions by Adsorption in Static and Dynamic Conditions on Activated Carbons in Aqueous Media

This work investigated the removal, kinetics and thermodynamics of iron(II) ions (Fe(II)) by adsorption in static and dynamic conditions in aqueous media on activated carbons (AC-i30min, AC-i1h, and AC-i24h), prepared from palm nut shells collected in the city of Franceville to Gabon, using potassium hydroxide (KOH) as the activating agent. Results on the elimination of Fe(II) in static and dynamic adsorption on prepared activated carbons (ACs) showed that the AC-i24h adsorbent has the best Fe(II) adsorption capacities at saturation (Qsat). The Qsat obtained on AC-i24h in static and dynamic conditions (17.87 and 10.38 mg/g, respectively) were higher than those of AC-i30min (13.89 and 5.54 mg/g respectively) and AC-i1h (14.92 and 8.64 mg/g respectively). Moreover, the static adsorption was more effective in the removal of Fe(II) ions in aqueous media in our experimental conditions. The percentage removal (%E) of Fe(II) obtained on prepared activated carbons in static conditions was better than those obtained in dynamic conditions, especially on AC-i24h, where the %E was 89.27% in static and 61.56% in dynamic. In kinetics, results showed that the pseudo-second-order kinetic model best described the adsorption mechanisms of Fe(II) on prepared activated carbons in static adsorption, with mainly of chemisorption on the solid surfaces. However, in dynamic conditions, the pseudo-first-order kinetic model was more suitable. In addition to the weak interactions between Fe(II) and the activated carbon surfaces, strong interactions (chemisorption) were also observed. Also, thermodynamic data obtained on AC-i24h in static adsorption indicated that the adsorption of Fe(II) was spontaneous and increased with temperature (ΔG˚ H˚ = 503.54 KJ/mol).

Effects of coal rank, Fe_3O_4 amounts and activation temperature on the preparation and characteristics of magnetic activated carbon

Coal-based Magnetic Activated Carbons （CMAC＇s） were prepared from three representative coal samples of various ranks： Baorigele lignite from Inner Mongolia; Datong bitumite from Shanxi province; and Taixi anthracite from Ningxia Hui Auto- nomous Region. Fe3O4 was used as a magnetic additive. A nitrogen-adsorption analyzer was used to determine the specific surface area and pore structure of the resulting activated carbons. The adsorption capacity was assessed by the adsorption of iodine and methylene blue. X-ray diffraction was used to measure the evolution behavior of Fe304 during the preparation process. Magnetic properties were characterized with a vibrating-sample magnetometer. The effect of the activation temperature on the performance of CMAC＇s was also studied. The results show that, compared to Baorigele lignite and Taixi anthracite, the Datong bitumite is more appropriate for the preparation of CMAC＇s with a high specific surface area, an advanced pore structure and suitable magnetic properties. Fe304 can effectively enhance the magnetic properties and control the pore structure by increasing the ratio of meso- pores. An addition of 6.0% Fe304 and an activation temperature of 880 ℃ produced a CMAC having a specific surface area, an iodine adsorption, a methylene blue adsorption and a specific saturation magnetization of 1152.0 m2/g, 1216.7 mg/g, 229.5 mg/g and 4.623 emu/g, respectively. The coal used to prepare this specimen was Datong bitumite.

Modification Mechanism of Coconut Husk Activated Carbon Using FeSO4 and Fe(NO3)3

Modification conditions determine the surface topography and the active material phase composition of a catalyst.To study the influence of modification on a carbon-based sorbent,coconut husk activated carbon(AC)which was activated using HNO3 and modified by FeSO4 and Fe(NO3)3 was examined.The pore textures and surface chemical characteristics of the carbon materials were examined by scanning electron microscopy(SEM),Brunner-Emmet-Teller(BET),X-ray diffraction(XRD)and Fourier transform infrared(FTIR)spectroscopy.The surface topography,the pore structure,active materials,and functional groups of AC,AC modificated by HNO3(HNO3/AC for short),and AC modificated by FeSO4 and Fe(NO3)3(Fe/AC for short)were systematically studied.Subsequently,the mechanism of modifying the conditions for the carbon materials was determined.Results showed that the surface micro topography of HNO3/AC became unsystematic and disordered.After modification with FeSO4,the ferriferous oxide was mainly present as a near-spherical crystal.Ferriferous oxides from Fe(NO3)3 modification mainly exhibited a plate shape.HNO3 modification could enlarge the pores but decrease the specific surface area of AC.FeSO4 modification resulted in a new net post structure in the pore canal of AC.Fe(NO3)3 modification caused the pore space structure to develop in the interior,and a higher calcination temperature was useful for ablation.The ash content of the AC was substantially reduced upon HNO3 modification.Upon FeSO4 modification,α-FeOOH,α-Fe2O3 andγ-Fe2O3 coexisted under the condition of a lower concentration of FeSO4 and a lower calcination temperature,and a higher FeSO4 concentration and calcination temperature generated moreα-Fe2O3.The same Fe(NO3)3 modification and a higher calcination temperature were beneficial to the minor chipping formation ofγ-Fe2O3.A higher Fe(NO3)3 loading produced a lower graphitization degree.HNO3 modification formed various new oxygen-containing functional groups and few nitrogen-containing groups.Based on the cover,FeSO4 and Fe(NO3)3 modification could decrease the oxygen-containing and nitrogen-containing functional groups.These results could optimize the modification condition and improve physical and chemical properties of carbon-based sorbents.

Fast adsorption of microcystin-LR by Fe(Ⅲ)-modified powdered activated carbon

Microcystins(MCs) are cyclic hepatotoxic peptides produced by the bloom-forming cyanobacterium Microcystis and present a public health hazard to humans and livestock. The removal of MCs from contaminated water with powdered activated carbon(PAC) has been employed as a simple and economic treatment strategy. In this study, PAC-Fe(Ⅲ) was prepared and utilized for the fast and efficient removal of MCs from water. PAC-Fe(Ⅲ) exhibited superior microcystin-LR(MC-LR) removal capacity and efficiency compared to the unmodified PAC. The MC-LR removal efficiency of PAC-Fe(Ⅲ) increased with decreasing p H within the pH range of 4.3 to 9.6. PAC-Fe(Ⅲ) could be reused for 3 times by methanol elution while the MC-LR removal efficiency was still over 70 percent. The removal efficiency was positively correlated to the ionic strength of water and negatively correlated to alkalinity. Natural organic matter(NOM) such as humic acid(HA) and salicylic acid(SA) generated low interference with MC-LR adsorption by PAC-Fe(Ⅲ). The complexation reaction between Fe^(3+) in PAC-Fe(Ⅲ) and the functional groups of MCLR was suggested as the key mechanism of MC-LR removal by PAC-Fe(Ⅲ). The results suggest that Femodified PAC is a promising material for the treatment of MC-contaminated waters.

MIL-100(Fe^(Ⅱ)/Fe^(Ⅲ))/ACF复合材料的制备及光催化脱色性能

以七水合硫酸亚铁和无水硫酸铁为金属盐,均苯三甲酸为配体,活性碳纤维(ACF)为基材,在室温下采用原位生长法制备了MIL-100(Fe^(Ⅱ)/Fe^(Ⅲ))/ACF复合材料。研究了复合材料的制备工艺和应用工艺对活性艳蓝KN-R光催化脱色效果的影响,并探讨了其光催化脱色的机理。结果表明:Fe2+与Fe3+的摩尔比为3∶1,原位生长20h条件下制备的复合材料,在1000W氙灯光照下处理120min,对加入0.32mL/L H_(2)O_(2)、pH为3.0、浓度为80mg/L的活性艳蓝KN-R染液的脱色率可达97.1%以上,而且在染液pH=3.0~6.2的范围内脱色率均在95.8%以上,重复使用5次后脱色率有所降低,但仍然可达85.5%。通过自由基捕获实验,发现在光催化体系中起主要作用的是羟基自由基(·OH)和光生空穴(h+)。采用扫描电子显微镜(SEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)对复合材料进行了表征,结果显示MIL-100(Fe^(Ⅱ)/Fe^(Ⅲ))成功负载在ACF上,与MIL-100(FeⅡ)/ACF相比,MIL-100(Fe^(Ⅱ)/Fe^(Ⅲ))/ACF的活性位点的结合能要高0.2~0.3eV。

Preparation and Supercapacitive Properties of Fe_2O_3/Active Carbon Nanocomposites

Fe2O3/active carbon（Fe2O3/AC） nanocomposites were readily fabricated by pyrolyzing Fe3＋ impregnated active carbon in a nitrogen atmosphere. The as-prepared composites were studied by X-ray powder diffraction（XRD）, X-ray photoelectron spectroscopy（XPS） and transmission electron microscopy（TEM）. The capacitive property of the composites was investigated by cyclic voltammetry（CV） and galvanostatic charge-discharge test. Physical characterizations show that the γ-Fe2O3 fine grains dispersed in the AC well, with a mean size of 21.24 nm. Electrochemical tests in 6 mol/L KOH solutions indicate that the as-prepared nanocomposites exhibited improved capacitive properties. The specific capacitance（SC） of Fe2O3/AC nanocomposites was up to 188.4 F/g that was derived from both electrochemical double-layer capacitance and pseudo-capacitance, which was 78% larger than that of pristine AC. A symmetric capacitor with Fe2O3/AC nanocomposites as electrode showed an excellent cycling stability. The SC was only reduced by a factor of 9.2% after 2000 cycles at a current density of 1 A/g.

Adsorption-oxidation of hydrogen sulfide on Fe/walnut-shell activated carbon surface modified by NH_3-plasma

Walnut-shell activated carbon（WSAC） supported ferric oxide was modified by non-thermal plasma（NTP）, and the removal efficiency for hydrogen sulfide over Fe/WSAC modified by dielectric barrier discharge（DBD） was significantly promoted. The sample modified for10 min and 6.8 k V output（30 V input voltage） maintained 100% H2 S conversion over a long reaction time of 390 min. The surface properties of adsorbents modified by NTP under different conditions were evaluated by the methods of X-ray photoelectron spectroscopy（XPS）, Brunauer–Emmett–Teller（BET） analysis and in-situ Fourier transform infrared spectroscopy（FTIR）, to help understand the effect of the NTP treatment. NTP treatment enhanced the adsorption capacity of Fe/WSAC, which could due to the formation of micro-pores with sizes of0.4, 0.5 and 0.75 nm. XPS revealed that chemisorbed oxygen changed into lattice oxygen after NTP treatment, and lattice oxygen is beneficial for H2 S oxidation. From the in-situ FTIR result,transformation of the reaction path on Fe/WSAC was observed after NTP modification. The research results indicate that NTP is an effective method to improve the surface properties of the Fe/WSAC catalyst for H2 S adsorption-oxidation.

Low-temperature Denitration Mechanism of NH_(3)-SCR over Fe/AC Catalyst

To study the modification mechanism of activated carbon(AC)by Fe and the low-temperature NH_(3)-selective catalytic reduction(SCR)denitration mechanism of Fe/AC catalysts,Fe/AC catalysts were prepared using coconut shell AC activated by nitric acid as the support and iron oxide as the active component.The crystal structure,surface morphology,pore structure,functional groups and valence states of the active components of Fe/AC catalysts were characterised by X-ray diffraction,scanning electron microscopy,nitrogen adsorption and desorption,Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy,respectively.The effect of Fe loading and calcination temperature on the low-temperature denitration of NH_(3)-SCR over Fe/AC catalysts was studied using NH_(3)as the reducing gas at low temperature(150℃).The results show that the iron oxide on the Fe/AC catalyst is spherical and uniformly dispersed on the surface of AC,thereby improving the crystallisation performance and increasing the number of active sites and specific surface area on AC in contact with the reaction gas.Hence,a rapid NH_(3)-SCR reaction was realised.When the roasting temperature remains constant,the iron oxide crystals formed by increasing the amount of loading can enter the AC pore structure and accumulate to form more micropores.When the roasting temperature is raised from 400 to 500℃,the iron oxide is mainly transformed fromα-Fe_(2)O_(3)toγ-Fe_(2)O_(3),which improves the iron oxide dispersion and increases its denitration active site,allowing gas adsorption.When the Fe loading amount is 10%,and the roasting temperature is 500℃,the NO removal rate of the Fe/AC catalyst can reach 95%.According to the study,the low-temperature NH_(3)-SCR mechanism of Fe/AC catalyst is proposed,in which the redox reaction between Fe~(2+)and Fe~(3+)will facilitate the formation of reactive oxygen vacancies,which increases the amount of oxygen adsorption on the surface,especially the increase in surface acid sites,and promotes and adsorbs more reaction gases(NH_(3),O_(2),NO).The transformation from the standard SCR reaction to the fast SCR reaction is accelerated.

Fe/活性炭多相类Fenton法湿式氧化罗丹明B废水的研究

采用自制的Fe/活性炭(Fe/AC)为催化剂,H2O2为氧化剂,组成多相类Fenton试剂催化降解罗丹明B染料废水。实验结果表明,在催化剂加入量为0.8 g/L,H2O2体积分数为0.3%,废水pH值为13,反应时间为30 min的条件下,质量浓度为200 mg/L的罗丹明B染料废水的脱色率达100%。反应动力学研究表明,罗丹明B脱色反应近似为一级反应,30℃时反应速率常数为0.02675 min-1,表观活化能为69.47 kJ/mol。

Fe对Pt-Fe/C催化剂电催化氧还原反应活性的影响

制备了用作直接甲醇燃料电池的碳载Pt-Fe(Pt-Fe/C)阴极催化剂,X射线能量色散谱(EDX)、X射线衍射谱和电化学测量的结果表明,在Pt-Fe/C催化剂中,Fe以3种形式存在.质量分数大约为20%的Fe进入Pt的晶格,形成Pt-Fe合金,质量分数大约为80%的Fe没有进入Pt的晶格而以Fe和Fe2O3的形式单独存在.该催化剂经酸处理后,非合金化Fe和Fe2O3被溶解,而使Pt-Fe/C催化剂的电化学活性比表面积要比未经酸处理前的增加约30%左右,导致Pt-Fe/C催化剂对氧还原的电催化活性优于未经酸处理前的Pt-Fe/C催化剂.研究结果表明,Pt-Fe/C催化剂的电化学活性比表面积对氧还原的电催化活性起重要的作用,另外,只有与Pt形成合金的Fe能提高Pt对氧还原的电催化活性,而非合金化的Fe对Pt催化剂对氧还原的电催化活性基本没有影响.

原生/酸洗活性炭负载Fe-Ni催化剂对松木气化制备合成气的影响

活性炭(AC)经HCl溶液处理得到酸洗活性炭(AWAC),利用超声浸渍法将Fe-Ni活性组分负载于AC与AWAC上,研究催化剂AWAC,AC,Fe-Ni/AWAC和Fe-Ni/AC对松木气化制备合成气的影响,并采用EDS-SEM,BET,XRD,FTIR和XPS等表征方法研究催化剂的性质与变化。研究结果表明:超声浸渍法可将FeNi合金成功负载于炭载体上,气化反应过程中催化剂催化活性的排序为Fe-Ni/AC>Fe-Ni/AWAC>AC>AWAC;当Fe-Ni/AC为催化剂时,H_(2)体积分数为46.46%,合成气的H_(2)/CO为1.97,气体总产量可达6.38 L;Fe-Ni/AC中固有的AAEMs元素不仅对Fe-Ni组分的催化活性具有促进作用,还有助于抑制活性组分的烧结和团聚;炭载体上的含氧官能团对松木挥发分具有重整作用,其中C-O基团为主要的反应活性位点之一。

一步火焰辅助热解法制备Fe掺杂嵌碳TiO_2及其光催化性能

以钛酸四丁酯、无水乙醇和无水氯化铁为前驱体,通过一步火焰辅助热解法制备了Fe掺杂嵌碳TiO2,并研究了样品的光催化活性.利用扫描电子显微镜及能谱、X射线光电子能谱、X射线粉末衍射和紫外-可见漫反射吸收光谱等对样品的形貌、组分、晶型和光吸收进行了表征,并研究了样品在紫外和可见光下的光催化活性.结果表明,无需后续热处理可直接得到主要是锐钛矿相TiO2的样品,Fe3+以替位掺杂形式进入TiO2晶格,随掺杂量增加,样品在可见光区域的吸光度提高,吸收带边红移.Fe掺杂量(摩尔分数)小于0.2%可改善样品的光催化活性,当Fe掺杂量为0.1%时,样品在可见光和紫外-可见光照射下均显示出最高的降解亚甲基蓝速率.

不同淹水时间水稻土微生物群落的Fe(Ⅲ)还原能力及其与脱氢酶活性的关系

为探讨淹水水稻土中微生物Fe(Ⅲ)还原机理,采用厌氧恒温培养方法,比较了水稻土微生物群落在淹水演替过程中,分别以葡萄糖、丙酮酸盐和乳酸盐为底物时的脱氢酶活性变化及Fe(Ⅲ)还原特征.结果显示,不同淹水时间的土壤微生物群落均可以葡萄糖为优势碳源还原Fe(OH)3,最大反应速率对应时间(TVmax)与脱氢酶活性峰值出现时间比较一致,为厌氧培养的6—8d;以丙酮酸盐或乳酸盐为碳源时,脱氢酶活性的半饱和常数Ks表现为淹水30d<12d<1d,Fe(Ⅲ)还原过程和脱氢酶活性均随淹水时间延长而显著增强;Fe(Ⅱ)生成量在91—345mg/L时,土壤脱氢酶具有最大活性.本试验表明,利用葡萄糖的脱氢过程主要发生在厌氧培养初期,脱氢酶活性是影响水稻土中Fe(Ⅲ)还原过程的重要因素;脱氢酶活性峰值出现时间与Fe(Ⅲ)还原最大反应速率Vmax呈显著负相关关系,与TVmax则为显著正相关.

“Fe-Au-Sb-S”体系中金迁移规律的实验研究

在黔滇桂微细浸染型金矿地质研究及前人实验研究基础上设计了７５℃含碳的“Ｆｅ－Ａｕ－Ｓｂ－Ｓ”热液开放流动体系实验，测定带出溶液之ｐＨ及Ａｕ、Ｆｅ、Ｓｂ含量，研究Ａｕ、Ｆｅ、Ｓｂ的迁移条件及相互关系。探讨本区主成矿期之后叠加热液活动中金与锑的行为及金异常与锑异常既密切共生。

合成气转化为低碳烯烃Fe/活性炭催化剂制备及性能表征

本研究以活性炭作为载体制备铁基催化剂 ,通过对不同铁盐、活性炭、助剂的筛选 ,研制出具有高活性和高选择性的合成气转化为低碳烯烃催化剂。对反应前及反应过程中催化体相结构的XRD测试结果表明 ,Fe—Cu—K/活性炭催化剂反应前主要由α -Fe、Fe3O4 以及CuO组成 ,经与合成气反应转变为α -Fe、Fe5C2 、、Fe7C3、CuO和K2 O。Fe—Mn—K/活性炭催化剂的晶体结构主要以Fe嵌入MnO当中形成的 (Fe ,Mn)O结构存在。实验中得出的α -Fe、FexCy 以及 (Fe ,Mn)O与激光热解法制备的催化剂的的晶体结构相似。对催化剂的制备方法进行了筛选 ,考察了不同助剂Cu、Mn、Si、K等元素对催化性能的影响 ,结果表明以草酸铁为铁盐 ,椰壳炭为载体的Fe—Mn—K/活性炭催化剂的催化效果最佳 ,在 1.5MPa、32 0℃、空速 6 0 0h- 1条件下作催化性能测试 ,CO转化率达到 97.4 %以上 ,C=2 ～C=4 选择性达到 6 8%以上。

印染废水的活性炭负载Fe离子掺杂TiO_2光催化降解

采用溶胶-凝胶法制备了活性炭(AC)负载Fe离子掺杂的TiO_2光催化剂(Fe-TiO_2/AC),并对其进行了XRD、N2吸附-脱附和XPS等表征,通过光催化降解印染二级废水,考察其催化性能。结果表明,1.5%Fe-TiO_2/AC的光催化性能最佳,催化剂中TiO_2平均粒径为17.6 nm,比表面积为887.11 m^2/g,Fe离子在催化剂中存在Fe^(3+)和Fe^(2+)两种价态。考察了焙烧温度、催化剂投加量等因素对催化活性的影响,发现当焙烧温度为500℃,反应时间为5 h,催化剂添加量为5 g/L时,催化效果最佳,COD去除率可达70.31%。催化剂重复使用6次后,催化活性为62.37%。

Fe—C—j(j=Ti,V,Cr,Mn)熔体的热力学性质规律

利用本文提出的热力学性质方法，根据Ｆｅ－Ｃ－ｊ（ｊ＝Ｔｉ，Ｖ，Ｃｒ，Ｍｎ）熔体中的Ｃ溶解度与温度及第三组元ｊ之间的关系式，研究了Ｆｅ－Ｃ－ｊ熔体中第三组元ｊ对Ｃ溶解度的影响因子ｋｉ；ｍｊ以及组元的活度相互作用系数与第三组元ｊ原子序数间的关系，探讨了 Ｆｅ－Ｃ－ｊ（ｊ＝Ｔｉ，Ｖ，Ｃｒ，Ｍｎ）熔体中不同组元热力学性质的变化规律．

活性炭颗粒稳定化纳米级Pd/Fe复合颗粒对2-氯联苯的还原脱氯

利用超声波强化液相还原法制备活性炭颗粒(GAC)稳定化纳米级Pd/Fe复合颗粒,并对2-氯联苯(2-CB)进行催化还原脱氯研究。结果表明:40k Hz超声波辐照强化下制备的GAC稳定化纳米级Pd/Fe复合颗粒的比表面积、粒径和分散性均较普通液相还原法制备的复合颗粒有明显改善,粒径均在100nm以下,比表面积增大了21.73%。当复合颗粒钯化率为0.3%(质量分数)且GAC和Pd/Fe投加量分别为0.15g/L和5.0g/L时,在反应温度25℃、初始pH为3的条件下反应300min后,对初始质量浓度为10mg/L的2-CB降解率近95%,符合拟一级反应动力学,反应速率常数为3.88×10^(–2)min^(–1)。

Fe/活性炭催化湿式过氧化氢氧化亚甲基蓝

以活性炭为载体,采用浸渍法制备Fe/AC催化剂,通过扫描电镜、X射线衍射对催化剂进行表征,研究AC以及Fe/AC催化湿式过氧化氢氧化亚甲基蓝的性能,考察了反应温度对其催化性能的影响。结果显示:Fe/AC对亚甲基蓝的去除率达99%,COD去除率达86%,处理后水样COD值达到GB 8978—1996《污水综合排放标准》二级排放标准。