生物质基炭膜电吸附去除水中Pb(Ⅱ)的研究

利用二层牛皮为原料,经炭化、硝酸氧化和水蒸气活化制备改性生物质基炭膜。采用比表面积及孔径分析仪、傅里叶红外光谱技术(FT-IR)、Boehm滴定法对生物质基炭膜的物理化学特性进行表征。以生物质基炭膜为电极材料,采用电吸附去除废水中Pb(Ⅱ),分别研究电压、电极板间距、初始Pb(Ⅱ)浓度对吸附效果的影响。结果表明,经硝酸氧化和水蒸气活化后的炭膜,其比表面积、总孔体积及含氧官能团均明显增加。改性后生物质基炭膜电极对Pb(Ⅱ)的去除率是未改性生物质基炭膜电极的3.87倍,在电压3V,Pb(Ⅱ)初始浓度50mg/L,电极板间距25mm电吸附条件下,Pb(Ⅱ)去除率为46.53%,吸附容量为48.08mg/g。该炭膜能够再生和重复利用,但是炭膜稳定性还需进一步改进。电吸附过程符合准一级动力学模型。     

生物炭改性策略及其在铬(Ⅵ)污染修复中的研究进展

六价铬（Cr（Ⅵ））是自然环境中毒性很强的重金属污染物之一,对生态系统构成严重威胁。生物炭是生物质在缺氧条件下热解产生的一种富碳固体物质,因具有比表面积大、孔结构发达和官能团丰富等优点,可作为修复Cr（Ⅵ）污染的高效吸附材料。目前,研究人员主要通过物理改性、化学改性、负载金属改性及生物改性等多种策略进一步增强生物炭对Cr（Ⅵ）的吸附能力。本文综述了近年来生物炭改性的研究进展,系统梳理了不同生物炭改性策略,比较了不同改性策略制备的生物炭对Cr（Ⅵ）污染的修复效率,分析了其作用机制,并对生物炭的改性修饰及其在实际应用中的未来发展方向进行了讨论。     

不同改性方法对酒糟生物炭理化性质及其吸附能力的影响

本文以酒糟生物炭为供试材料,比较研究了化学活化改性法(HNO₃、NaOH和H₂O₂)、有机改性法(海藻酸钠和柠檬酸)以及金属盐或金属氧化物改性法(FeCl₃和Fe₂O₃)对酒糟生物炭理化性质及其吸附性能的影响,为制备高吸附性能生物炭提供理论依据。实验结果表明:(1)不同改性方法对酒糟生物炭吸附Cd(Ⅱ)能力影响较大。吸附实验结果显示,FeCl₃改性(C₁)显著降低酒糟生物炭的吸附能力,其他改性方法均提高生物炭的吸附能力。选取三类改性方法中吸附作用最好的一种进行比较,其中Fe₂O₃改性碳(C₂)对Cd(Ⅱ)的吸附作用最强,H₂O₂改性炭(A₃)次之,柠檬酸改性炭(B₂)效果最差,三种改性生物炭与对照相比分别提高了30.45%、13.49%和10.4%。(2)生物炭...     

活性炭电极材料的表面改性和性能

以硝酸、双氧水、氨水三种化学试剂分别对活性炭进行表面改性, 用N2吸附法和FTIR表征炭材料改性前后孔结构和表面官能团的变化. 制备了以改性活性炭为电极材料, KOH溶液为电解质的模拟双电层电容器. 用恒流充放电、循环伏安、交流阻抗等方法考察了双电层电容器的电化学性能. 结果表明, 改性活性炭比表面积和平均孔径有所降低, 并且在炭材料表面引入了含氧或含氮官能团, 如—OH、>CO、—NH2等, 使炭材料的润湿性增强、电阻减小、电化学性能显著提高. 用65%硝酸改性后炭材料的比容量最高达到250 F·g-1, 比原样炭提高了72.4%; 实验电容器的漏电流急剧下降, 只有3-18 μA, 为原来电容器的漏电流(371 μA)的0.8%-4.9%.     

介孔炭表面性质对吸附去除低浓度氨性能的影响

室内环境中低浓度氨污染普遍存在,影响人的身体健康,而消除这些低浓度的氨相对困难。本文报道了一种适用于低浓度氨吸附去除的介孔炭材料,其性能明显优于经硝酸处理的活性炭材料。该介孔炭采用磷酸铝为硬模板制备,炭表面存在大量含氧官能团,研究显示炭表面羧基和内酯基在吸附氨过程中发挥着重要作用,它们作为酸性中心与氨发生化学作用,可以有效地捕获空气中低浓度的氨污染物。     

生物炭去除水中四环素的研究进展

随着抗生素药物(如四环素)的大量使用,近几年抗生素的环境行为和毒性已经成为人们的研究焦点和热点.我国的地表水、地下水、市政污水、养殖废水等不同水体中都检测到了四环素等抗生素药物,引发的水生态问题受到了众多学者的广泛关注.生物炭因具有制备来源广泛且易得廉价、比表面积大、孔隙发达、官能团种类较多等优点被学者们重点关注,已有众多文献报道发现不同种生物炭对四环素的吸附具有优越的性能.本文综述了近年来不同生物质制备的生物炭对四环素的吸附影响以及不同水化条件对四环素对生物炭吸附特征的影响,并阐述了生物炭吸附四环素过程中所涉及的机理.对进一步探究生物炭对四环素吸附的影响具有一定的指导意义.     

焙烧态镁铁水滑石改性生物炭吸附磷酸盐特性

以废弃的菠菜叶作为生物炭原料,采用简单的共沉淀法制备出焙烧态镁铁水滑石改性的生物炭复合材料(MFSL)。采用X射线衍射仪(XRD)、电子显微镜(SEM)、红外光谱仪(FT-IR)、N_2吸附-脱附(BET)和Zeta电位仪等技术对MFSL的结构、表面形貌、表面官能团性质,孔结构参数及零点电位值进行了表征,并考察了吸附时间、初始磷酸盐浓度、共存离子和溶液pH对MFSL吸附磷酸盐效果的影响。结果表明:MFSL具有良好的层状结构,比表面积为121.5 m~2·g~(-1)。Langmuir模型拟合得到MFSL对磷酸盐的最大吸附量可达115.10 mg·g~(-1),较原始生物炭提高了75%。MFSL对磷酸盐动力学吸附过程符合准二级动力学模型,吸附过程以化学作用为主。MFSL的零点电荷为9.64,在pH=3～9范围内对磷酸盐表现出较好的吸附性能。多组分干扰离子共存时,CO_3~(2-)和SO_4~(2-)相比K~+、Na~+和Cl~-对MFSL除磷性能抑制作用更大,Ca~(2+)则有略微促进作用。     

改性活性炭热反应安全性研究

针对活性炭吸附VOCs过程的安全性问题进行了研究,采用咪唑-脯氨酸离子液体对活性炭进行改性,优化吸附性能。以典型的甲苯气体为例,讨论了改性前后活性炭结构的变化对甲苯吸附性能的影响,并探索了改性前后活性炭的热反应安全性。研究结果表明:咪唑-脯氨酸改性活性炭表面的孔隙数量增多、孔径变大、含氧官能团增加、比表面积和体积增大。改性活性炭对甲苯的吸附量78 mg·g~(-1)是改性前活性炭吸附量36.03 mg·g~(-1)的2.17倍,吸附能力明显提升;粒径为51μm和111μm的两种改性活性炭的自燃温度比未改性活性炭的自燃温度分别提高了22.4℃和19.4℃且到达自燃温度所需时间分别延长了11.17 h和0.75 h。改性活性炭所需活化能为47.32kJ·moL~(-1),热稳定性优于未改性活性炭。     

ZnCl2、KOH和HNO3改性MWCNT对苯酚的吸附行为研究

通过扫描电子显微镜、X射线衍射仪、N₂吸附分析仪及Boehm滴定法获得ZnCl₂、KOH和HNO₃化学处理对高纯多壁碳纳米管的结构和表面含氧官能团的影响,通过批处理实验考察吸附条件（吸附时间、初始浓度、温度）对处理前后的碳纳米管吸附苯酚行为的影响,并采用准一级、准二级、Evolich动力学模型和热力学方程拟合其吸附数据,分析其动力学行为、热力学行为和吸附机理。结果表明,虽然ZnCl₂、KOH和HNO₃化学处理法均未对碳纳米管BET比表面积产生显著影响,但会影响其表面化学性质（即,对于ZnCl₂和KOH化学处理降低表面羧基、内酯基含量和增大碱性官能团量,而对于HNO₃化学处理可以增大表面羧基、内酯基含量,而碱性官能团略有增加）;改性处理影响碳纳米管去除苯酚效率：由于ZnCl₂和KOH改性处理降低碳纳米管表面羧基量,故其提高了苯酚去除率,而HNO₃处理则略减小碳纳米管的苯酚去除率,可能是由于碳纳米管结构和表面化学性质共同影响所致;碳纳米管的苯酚去除率均随苯酚溶液初始浓度的增大而减小;高温不利于吸附;热力学研究发现碳纳米管吸附苯酚过程是自发的和放热的,属于物理吸附;动力学研究表明,吸附过程符合准二级动力学方程。通过ZnCl₂和KOH化学处理,可以显著提高碳纳米管对苯酚的吸附性能。     

白酒酒糟生物炭的性质及对土壤无机磷释放的影响

为实现白酒酒糟的资源化利用,采用限氧热裂解技术制备酒糟生物炭,分析其理化性质,并通过淋溶实验研究了添加生物炭对土壤无机磷淋失的影响。结果表明,裂解温度为400°C时,酒糟生物炭裂解基本完成,生物炭产率、吸水率及灰分含量与裂解温度呈负相关,碳含量、比表面积及缺陷度(I_D/I_G)与热解温度呈正相关。生物炭中含有的官能团(-OH、-COOH、-C=O等)种类及数量随温度升高发生变化,且官能团中C-O键占比提高。土柱淋溶实验表明各个温度制备的酒糟生物炭均对土壤无机磷的释放有促进作用,其中,480°C裂解制备的生物炭(BC480)对土壤中无机磷的释放表现出最好的促进效果。因此,在400-600°C即可制备酒糟生物炭并用于土壤中促进无机磷的释放,为酒糟的资源化利用提供一种新的方式。     

生物质炭的制备、改性以及在挥发性有机物吸附方面的应用

挥发性有机物（VOCs）是大气中重要的污染源之一,对环境和人类健康产生严重的危害。吸附法是工业中最常用的去除VOCs的方法,吸附剂是吸附技术的关键,生物质炭是一种由生物质基材料在高温下热解活化等工艺制得的炭材料,具有较高的比表面积、丰富的孔隙结构和化学活性表面,在环境污染控制领域具有广泛应用。基于最近的研究,本文系统地综述了常用于去除VOCs的生物质炭的制备和改性方法,以及生物质炭在吸附VOCs的应用研究。本文首要目标是评估生物质炭去除VOCs的能力,特别是经过各种改性和活化工艺后,评价生物质炭作为吸附剂去除VOCs的适用性;确定改性和活化后对VOCs吸附能力的影响;揭示生物质炭对VOCs可能存在的吸附机理。最后,文章也对生物质炭的再生提出了建议和展望。     

Electrochemical devices obtained from biochar: Advances in renewable and environmentally-friendly technologies applied to analytical chemistry

Biochar is the carbon-rich material produced from organic feedstock such as agricultural wastes and municipal solid waste in limited oxygen atmosphere and under certain thermal combustion. Due to its high carbon content, high cation exchange capacity, large surface and stability structure, it has been applied in different field of knowledge. In relation to environment analytical chemistry the studies about biochar majorly focus in degradation of contaminants and soil and water remediation. However, due to its excellent electrical conductivity, biochar has been also applied to the manufacture of sensitive, robust, efficient and inexpensive devices applied to supercapacitor-based energy storage and chemically modified electrodes or sensors. Therefore, this review describes about obtention, modification and characterization of biochar as well as the pertinent aspects of electrochemical devises based on biochar and a general discussion about the environmental concern of biochar, challenges and prospects.     

Corncob-to-xylose residue (CCXR) derived porous biochar as an excellent adsorbent to remove organic dyes from wastewater

Biochar was prepared from corncob-to-xylose residue (CCXR) by KOH activation and anaerobic pyrolysis method. The effect of activation temperature on the microstructure of the biochar was studied. Results showed that the biochar prepared at 850°C (850NBC) possessed high specific surface area and exhibited excellent adsorption property. The maximum adsorption capacity of 2249 mg g⁻¹ was obtained when 850NBC was used for treating methylene blue (MB) solution. Adsorption isotherm fittings revealed that Langmuir and Freundlich models were applicable to 850NBC adsorption process, and the adsorption process was limited by adsorption site and the biochar surface functional groups. Furthermore, 850NBC showed good adsorption property when it was used to treat the other organic dyes of Congo red (751 mg g⁻¹), Orange II (735 mg g⁻¹), Indigo carmine (662 mg g⁻¹) and Methyl Orange (465 mg g⁻¹). Biochar 850NBC also possessed an acceptable recyclability which maintained 68.7% absorption capacity after 6 cycles when it was used to treat MB solution. These results proposed that 850NBC is expected to be a promising potential adsorbent for treating organic dyes waste water.     

Engineered biochar modified with iron as a new adsorbent for treatment of water contaminated by selenium

The purpose of this study was to develop an efficient method of biochar modification for effective removal of Se(VI) ions from water. Commercially available biochar produced from wheat straw was impregnated by Fe(NO₃)₃ (0.8, 4 and 10% w/v) and pyrolyzed at 200 °C. Optimum pH, adsorption kinetics, and Se(VI) adsorption isotherms were determined for the studied biochars. The modification significantly increased biochar’s ability for Se(VI) adsorption. The biochar modified with 10% Fe(NO₃)₃ has the highest adsorption effectiveness. The experimentally determined maximum adsorption capacity for the biochar modified with 10% Fe(NO₃)₃ was 14.3 mg g⁻¹ for pH 5, which was the optimum pH value. X-Ray Photoelectron Spectroscopy (XPS) and Photoacoustic Fourier Transform Infrared Spectroscopy (FTIR-PAS) investigation confirmed the presence of iron oxides/hydroxides on the surface of the modified biochar. The modification also resulted in the formation of oxygen containing functional groups. The study proved that the proposed modification can be efficient in increasing the biochar effectiveness in removing Se(VI) from water.     

透明质酸的改性及在生物医用材料领域的应用研究

透明质酸(HA)是人体内最为常见的一种粘多糖,具有优良的生物相容性和可降解性,可广泛应用于药物输送、皮肤填充材料、组织工程、药物载体和3D仿生学等方面,是当前生物医用材料领域的研究热点之一。HA具有独特的结构使其显示出特定的物理化学性质,可通过物理或化学方法修饰,赋予其新功能和新应用。本文从HA的分子结构出发,重点综述了HA的官能团羧基、羟基和乙酰胺基的化学改性和物理改性,主要包括羧基的酰胺化反应和酯化反应,羟基与环氧化物的开环反应、与有机硫化物的反应、酯化反应、与卤化物的反应和氧化反应,以及HA脱乙酰基反应;介绍了HA在生物医用材料领域的应用,并对其前景进行展望。     

Toward the design of efficient adsorbents for Hg2+ removal: Molecular and thermodynamic insights

A systematic DFT study was performed to evaluate the effect of oxygenated functional groups for Hg²⁺ adsorption in aqueous systems. This work includes several aspects usually neglected in many current works, namely, ground-state multiplicity, solvation effects, establishment of thermodynamic parameters, atomic charge transfer, and modeling of infrared spectra. In addition, two carbonaceous models were studied to account for both the effect of the carbonaceous matrix and the oxygenated functional groups on the Hg²⁺ binding. Adsorption energies indicated that Hg²⁺ adsorption on the unsaturated model is favored in the following order: phenol > lactone > semiquinone > carboxyl, whereas for the saturated model, the Hg²⁺ adsorption energy decrease order is: carboxyl > semiquinone > lactone. Thermodynamic parameters confirmed that the adsorption process is spontaneous (unsaturated model), while the infrared spectra provided an insight at the atomic level about the experimentally reported bands. Our results contributed to a deeper understanding of the current experimental information on the effect of the surface functional groups on the Hg²⁺ adsorption over carbonaceous materials as different active sites can be present on oxygenated carbonaceous materials for metal adsorption. The results also create new ways to improve the performance of adsorption capability of mercury and other pollutants.     

Study of a heavy metal biosorption onto raw and chemically modified Sargassum sp. via spectroscopic and modeling analysis

In this study, raw and formaldehyde-modified Sargassum sp. are used for heavy metal removal. A series of experiments shows that the chemical modification by formaldehyde improves biosorption capacity by approximately 20%. Solution pH plays an important role in the metal uptake. According to X-ray photoelectron spectroscopic and Fourier transform infrared spectroscopic analysis, the possible organic functional groups in the metal binding include carboxyl, ether, alcoholic, hydroxyl, and amino functional groups. A new model that includes a series of coordination reactions among a generalized functional group, alkaline earth metal ions and heavy metal ions, is developed for simulation of biosorption process. The model well describes the single- and multiple-species metal biosorption process under different conditions such as pH. The biosorption of heavy metals is due to the ion exchange between the heavy metals and alkaline earth metals and their adsorption onto the free sites of the seaweeds. Slightly more than half of the metal uptake is due to ion exchange. The metal affinity for the functional groups follows a descending order of lead > copper > alkaline earth metal.     

香蒲基生物炭的活化及对VOCs吸附的应用

以香蒲为原料制备生物炭(Biochar), 并用不同试剂进行活化. 活化前的Biochar比表面积和孔体积很小, 分别为1.71 m²/g和0.00421 cm³/g, 而活化后的Biochar比表面积和孔容均增大, 其中经碳酸钠（Na₂CO₃）活化后的Biochar比表面积和孔容最大. 研究了Na₂CO₃与Biochar的质量比对其活化的影响, 确定了Na₂CO₃/Biochar最佳质量比为3∶1条件下, 得到的样品Biochar-Na₂CO₃-3具有最优的表面积和孔容, 分别为624 m²/g和0.211 cm³/g, 并具有优异的挥发性有机化合物(VOCs)吸附性能, 其正己烷、 甲苯和92号汽油的静态吸附容量分别为1.03, 0.814和0.751 g/g, 正己烷和甲苯的动态吸附容量分别为1.00和0.796 g/g, 且吸附稳定性相对较高, 优于商业用活性炭(AC)和硅胶(SG).     

纳米氧化锌的机械力化学表面改性

采用机械力化学表面改性工艺,以硬脂酸为改性剂,在气流粉碎机中对纳米氧化锌进行解团聚和表面改性,并借助SEM、XRD、FF—IR和XPS对改性前后的氧化锌粉体进行结构表征．结果表明：硬脂酸分子化学键合在氧化锌表面．改性前后氧化锌的晶体结构相同,其颗粒的团聚性降低,二次粒径明显减小．通过测定改性样品的活化指数和亲油化度,选择最佳的改性剂用量为氧化锌质量的10％,氧化锌表面亲油疏水,在有机溶剂中有较好的分散性．     

Cadmium removal from aqueous solution by biochar obtained by co-pyrolysis of sewage sludge with tea waste

Resource utilization is a critical pathway for sustainable solid waste treatment. Biochar was prepared from the co-pyrolysis of sewage sludge and tea waste. Brunauer–Emmett–Teller measurement, scanning electron microscopy and Fourier transform infrared analysis were employed to characterize the biochar. Then, the interface behavior between biochar and Cd from aqueous solution was investigated. The effect of adsorbent dose and pH on Cd adsorption was evaluated. Adsorption kinetics and the adsorption isotherm were studied, and the adsorption mechanism was explored. The results showed that the suitable adsorbent dose was 4 g L^?1 and the optimal pH of the Cd solution remained at 6.0. Cadmium sorption on the biochar could be well described by the pseudo-second order kinetic model (R ² > 0.98). The adsorption process was described using the Langmuir (R ² > 0.86), Freundlich (R ² > 0.86), Temkin (R ² > 0.84) and Dubinin–Radushkevich (R ² > 0.86) isotherm models. The proportion of organic constituents in biochar was 69.2–72.4%. Minerals that originated in biochar played an important role during the Cd adsorption process, and the contribution of minerals accounted for 27.6–30.8% of the total adsorption. The main mechanism of the Cd adsorption process by biochar involved ion exchange, surface complexation, electrostatic interaction, surface co-precipitation, and other mechanisms. Therefore, biochar created by the co-pyrolysis of sewage sludge and tea waste could be used as an adsorbent for the removal of metal ions from contaminated water.