生物炭理化性质对其反应活性的影响

生物炭作为一种富炭材料,由于其具有固碳、增强土壤肥力、促进植物生长等特性,在固碳减排及土壤改良方面的应用价值受到广泛关注.同时,生物炭具有较大的比表面积和较高的孔隙率,常被作为吸附剂用于污染物的去除.研究发现生物炭在吸附有机污染物的过程中可降解有机污染物,因此生物炭的反应活性成为近年来研究的热点.生物炭的反应活性主要由其制备过程中生成的环境持久性自由基(EPFRs)和自身的氧化还原能力贡献.生物炭的EPFRs活性与官能团种类、过渡金属含量和EPFRs种类有关,其中官能团和过渡金属通过影响EPFRs的生成及稳定从而影响EPFRs的浓度和种类,进而影响EPFRs活性,而EPFRs种类直接影响EPFRs活性.生物炭的氧化还原活性与官能团、芳香性和导电性有关,其中官能团影响氧化还原活性基团(RAMs)的生成,芳香性和导电性影响基质电导(EC_(BC))结构的生成及导电活性,从而影响氧化还原活性.本文总结了生物炭的反应活性机理和影响因素,旨在为生物炭处理有机物污染物等方面的应用提供理论支撑和技术参考.     

不同温度生物炭酸化前后的表面特性及镉溶液吸附能力比较

以稻秆为原料,在不同温度(300,400,500,600,700℃)条件下采用限氧控温炭化制备生物炭,用HCl和HF对其进行酸化处理,利用傅立叶变换红外光谱仪、比表面积和孔径测定仪现代分析手段对生物炭酸化前后的表面官能团、比表面积、孔径等特性进行比较,分析制备温度和生物炭表面特性之间的关系,探究制备所需生物炭的最佳温度条件。通过生物炭酸化处理和镉吸附实验结果,研究酸可溶矿物在生物炭吸附镉的贡献及制备温度对生物炭吸附镉能力的影响,为生物炭吸附水体中重金属镉提供科学依据。傅里叶红外分析表明,不同温度生物炭表面官能团存在一定的差异,主要表现为随制备温度升高,烷烃基缺失,甲基-CH3和亚甲基-CH2逐渐消失,形成了芳香环且芳香化程度增加。生物炭酸化后无机矿物Si O2吸收峰逐渐消失,官能团种类并没有发生变化,不同官能团随制备温度变化规律仍与酸化前生物炭一致。表面积及孔径分析结果表明,生物炭孔结构主要为中孔,随着热解温度的升高,比表面积和总孔容有所增大,在600℃达到最大;平均孔径随着制备温度升高而变小。生物炭酸化处理可以显著增大生物炭比表面积,总孔容也有所增加。生物炭酸化后充分去除了矿物质,孔隙结构未发生变化,孔结构仍为中孔,微孔表面积减小。镉吸附实验表明生物炭对镉具有较强的吸附能力,不同温度条件下镉吸附率均高于75%,且随温度升高而上升。生物炭经酸化处理后,镉吸附能力显著下降,这说明生物炭中的酸可溶矿物质在镉溶液的吸附过程中有重要作用。     

裂解温度对稻秆与稻壳制备生物炭表面官能团的影响

以稻秆和稻壳为原料,在不同温度下(300、400、500、600、700℃)采用热裂解法制备生物炭,利用比表面积及孔径分析仪测定各生物炭比表面积,以傅里叶红外光谱图(FTIR)和Boehm滴定法分别定性和定量分析不同生物炭表面官能团的种类和数量,分析不同温度对不同原材料制备生物炭的表面官能团种类和数量的影响.结果表明,中、低温裂解条件(300、400、500℃)下,同温度稻壳生物炭(RC-H)比表面积显著高于稻秆生物炭(RC-S);高温裂解(600、700℃)条件下,同温度RC-S比表面积则更大.随裂解温度升高,两种原材料制备的生物炭比表面积均呈显著增大的趋势,其中稻秆在600℃下制备的RC-S比表面积最大,稻壳在700℃下制备的RC-H比表面积最大.FTIR分析结果显示,同一温度下两种材料制备的生物炭特征吸收峰基本相同,且表面基团种类大致相同,但RC-S较RC-H表面官能团更丰富,在热解过程中均形成了芳香环结构,且芳香化程度随裂解温度升高而增加.不同裂解温度下两种材料的生物炭表面官能团变化规律相似,主要表现为烷烃基随裂解温度升高而缺失,甲基(—CH3)和亚甲基(—CH2)逐渐消失,而芳香族化合物增加,芳香化程度增强.Bohem滴定结果表明,各裂解温度下RC-S的表面官能团总量和碱性官能团数量均高于RC-H,而各裂解温度下RC-S的酸性官能团含量均小于RC-H.随裂解温度升高,两种材料制备生物炭的表面官能团变化规律相似,表现为表面官能团总量均减少,酸性官能团含量降低,碱性官能团含量增加.     

导电性生物炭促进Geobacter和Methanosarcina共培养体系互营产甲烷过程

近年来研究发现互营氧化产甲烷过程中存在种间直接电子传递(direct interspecies electron transfer,DIET),这种电子传递方式比传统的种间氢转移或种间甲酸转移更为高效。导电生物炭作为导电介质,可以有效促进DIET介导的互营产甲烷进程。乙酸作为有机物厌氧降解的重要中间产物,其降解过程是否存在DIET途径尚不清楚,导电生物炭对乙酸互营降解产甲烷过程的影响机制也未有研究报道。以具有DIET功能的Geobacter sulfurreducens和Methanosarcina barkeri菌株为研究对象,构建共培养体系,以乙酸为电子供体,比较添加不同导电性生物炭共培养体系的甲烷产生和微生物生长情况。结果表明:(1)导电性生物炭处理的产甲烷速率为0.015~0.017 mmol?d~(-1),显著高于对照处理的0.012 mmol?d~(-1);而不导电生物炭处理的产甲烷速率低于对照处理。说明导电性生物炭促进共培养体系中的产甲烷过程,而不具导电性的生物炭没有促进效应;(2)导电性生物炭存在时,共培养体系的甲烷产生速率(0.008 mmol?d~(-1))和产量(0.14 mmol)明显高于Methanosarcina barkeri单菌体系的产甲烷速率(0.006 mmol?d~(-1))和产甲烷量(0.09 mmol),而添加不导电生物炭的共培养体系和单菌体系的甲烷产生速率和产量无明显差异。以上结果表明,导电性生物炭能介导Geobacter sulfurreducens和Methanosarcina barkeri之间的直接电子传递,即Geobacter sulfurreducens氧化乙酸产生的电子,以导电生物炭为导电通道直接传递至Methanosarcina barkeri还原CO2产生甲烷,从而促进乙酸互营氧化产甲烷过程。本研究结果有助于我们理解种间直接电子传递对互营产甲烷过程的贡献及影响效应,为研究甲烷产生的微生物机制提供新的研究思路。     

铂修饰电极催化氧化苯酚的热力学研究

研究苯酚在铂修饰玻碳电极上的电化学氧化.考察了温度、pH值和苯酚浓度对苯酚电化学氧化的影响.结果表明,随着温度的升高,苯酚的氧化峰电位逐渐减小,氧化峰电流逐渐增大;随着pH值的增大,氧化峰电位逐渐减小,峰电流开始逐渐减小,在pH7.5时突然增大,然后又减小;随着苯酚浓度的增大,苯酚的氧化峰电位逐渐减小,峰电流增大.苯酚在铂修饰电极上的电化学氧化反应活化能为14.6 kJ·mol-1.     

生物炭对土壤硝化反硝化微生物群落的影响研究进展

生物炭因具有发达的孔隙结构、丰富的表面官能团和无机矿物等特性,在控制农业面源污染和温室气体排放方面有着良好的应用前景.生物炭对氮循环微生物群落特征的影响是生物炭能否有效控制面源污染和改良土壤的核心问题.围绕生物炭对土壤氮循环微生物群落特征的影响,从生物炭的多元性、添加量和环境条件3个方面综述生物炭对土壤硝化和反硝化微生物的影响研究进展.高温热解生物炭对土壤氮循环微生物的积极作用要比低温热解生物炭效果好;生物炭原料来源、添加量对土壤氮循环微生物群落的影响存在较大差异;添加有机肥料要比常规化肥更能提高氮循环微生物碳源的利用能力及其活性;环境中的污染物如多环芳烃(PAHs)、酚类化合物(PHCs)和重金属等的存在不利于氮循环微生物的生存.随着分子生物技术的进步,未来应结合多种分子生态学技术和稳定同位素探针技术等手段研究生物炭对土壤氮循环微生物的影响机制,生物炭热解温度和添加量对土壤氮循环微生物的影响不容忽视,在长期的田间试验中应注意老化生物炭对污染物和氮循环微生物的影响.     

活性艳蓝X-BR的电化学行为及机理研究

采用循环伏安法、线性扫描伏安法及微分脉冲伏安法研究了活性艳蓝X BR在0 1mol·l- 1 KCl HCl溶液中的电化学行为 .研究发现 ,在 - 0 45V— 1 0VvsSCE电压范围内的循环过程中出现两对氧化还原电流峰 ,通过考察峰电压随溶液pH值的变化 ,提出了可能的电极反应机理 :阳极区的电极反应是属于失 1质子和 2电子的氧化反应 ,而阴极区的电极反应则是蒽醌基团被还原加氢成为氢醌基团的反应     

生物炭中溶解性有机质对污染物环境行为的影响

生物炭的广阔应用前景吸引了研究者的广泛关注。生物炭中具有显著流动性的溶解性有机质(Biochar-derived dissolved organic matter,BDOM)作为一种高效的吸附载体,对污染物迁移的影响显著,是了解生物炭环境效应的关键。然而,原料来源及热解温度与BDOM的特性之间的关联性,以及BDOM与污染物相互作用的机制尚未明确。因此,文章通过综述原料及热解温度对BDOM特性的影响,以明确BDOM影响污染物环境行为机制的研究现状。有关研究表明:(1)生物质原料中木质素含量越高,BDOM C含量越高,官能团种类更加丰富,芳香性更强,而产率则越低;(2)随热解温度的升高,BDOM中C含量增加、芳香性增强,而产率及含氧官能团种类降低;(3)BDOM与疏水性有机污染物形成致密的类胶体结构,使疏水性有机污染物的溶解度提高,从而使疏水性有机污染物更容易被降解;(4)BDOM通过增加土壤中溶解性有机质的含量,从而形成新的吸附位点(如羧基官能团),以促进土壤对重金属或有机污染物的固持;(5)BDOM与重金属发生络合或氧化还原作用,影响重金属形态,从而改变土壤中重金属的毒性和生物有效性。该文可为全面评估生物炭在土壤污染修复应用中的功能提供参考。     

三维多孔生物炭吸附剂的制备及其对菲的吸附行为

以生活中常见的丝瓜络为原材料,在氮气保护和不同温度(600、700、800、900℃)的条件下热解制备了三维多孔丝瓜络生物炭(LSBC600、LSBC700、LSBC800、LSBC900)。表征了丝瓜络生物炭的理化性质,通过动力学吸附实验和等温线吸附实验研究了不同热解温度条件下制备的丝瓜络生物炭对菲的吸附动力学特征和吸附等温线特征,探讨了可能的吸附机理,评估三维多孔生物炭对菲的去除能力,为水生态系统保护和饮用水安全提供科学依据。结果表明,热解温度会影响生物炭的表面官能团组成,进而影响其芳香性。丝瓜络生物炭呈现多管束堆叠的三维多孔结构,随着热解温度的升高,挥发性物质减少,丝瓜络生物炭的表面变得粗糙,比表面积增大,芳香结构增加;LSBC900的比表面积达到了467 m²·g^-1。吸附动力学结果说明,丝瓜络生物炭对菲的吸附是复杂和多阶段的,主导吸附速率的是液膜扩散过程,其次是颗粒内扩散过程。在600-900℃范围内,随着热解温度的升高,丝瓜络生物炭对菲的平衡吸附量升高,吸附速率加快。吸附等温线结果说明,热解温度升高可以提高丝瓜络生物炭对菲的吸附容...     

碳纳米管与分子印迹结合修饰玻碳电极应用于氯霉素的快速测定

为了研究水环境中氯霉素(CAP)的快速检测方法,用单壁碳纳米管(SWCNTs)-纳米铜(CuNPs)复合物修饰玻碳电极(GCE),并结合分子印迹(MIP)技术,先后采用循环伏安法(CV)进行电极导电性测试,线性伏安法(LSV)对实验条件进行优化,差分脉冲伏安法(DPV)研究水溶液中CAP的电化学行为.研究结果表明,与GCE电极相比,修饰电极上CAP氧化还原电流信号明显增强,表明修饰电极对CAP具有较好的选择性,能加速电子传递.同时对洗脱液类型、缓冲溶液pH、扫描速度、富集时间及修饰物的负载量等实验条件进行了优化.在最佳条件下,发现CAP还原峰电流大小与其浓度在5—500 nmol·L~(-1)范围内呈现良好的线性关系,线性方程为I(μA)=0.9204C+41.285(R~2=0.9984),检出限为4.8 nmol·L~(-1)(S/N=3),且该修饰电极具有良好的重现性和稳定性.将该修饰电极应用于实际样品分析时,氯霉素眼药水的加标回收率为95.1%—102.5%,实际地表水样的加标回收率为96.5%—102.1%.     

生物炭吸附有机污染物的研究进展

生物炭(biochar)是指生物质在缺氧条件下热裂解产生的一种产物.由于其精致的孔隙结构和独特的表面化学性质,对环境介质中的有机污染物有超强的吸附能力,进而影响污染物的迁移与归宿.近年来生物炭对有机污染物的吸附特性及机理研究已成为环境科学领域的研究热点之一.本文从生物炭的典型性状、吸附有机污染物的机理、影响因素以及对土壤中有机污染物生物可给性的影响等方面进行了综述,并提出生物炭吸附有机污染物未来的研究方向.     

Co-pyrolysis of sludge and kaolin/zeolite in a rotary kiln: Analysis of stabilizing heavy metals

• Adding kaolin/zeolite promotes the formation of stable heavy metals. • The potential ecological risk index of co-pyrolysis biochar is extremely low. • Increasing the pyrolysis temperature reduces the leaching toxicity of heavy metals. • The toxicity of biochar reduces with the increasing content of stable heavy metals. Pyrolysis is a promising technique used for treating of sewage sludge. However, the application of pyrolysis products is limited due to the presence of heavy metals. In this study, sewage sludge mixed with kaolin/zeolite was pyrolyzed in a rotary kiln, aiming to improve the immobilization of heavy metals in pyrolytic carbon. The total concentrations, speciation distributions, leaching toxicities, and potential ecological risk indices of heavy metals in pyrolysis biochar were explored to examine the effects of kaolin/zeolite and pyrolytic temperature on immobilizing heavy metals. Further, mineral composition and surface morphology of biochar were characterized by X-ray diffraction and scanning electron microscopy to reveal the potential mechanism of immobilizing heavy metals. Increasing pyrolysis temperature facilitated the stabilization of heavy metals in pyrolysis biochar. The proportions of stable heavy metals in biochar obtained at 650℃ were 54.50% (Cu), 29.73% (Zn), 79.29% (Cd), 68.17% (Pb) and 86.70% (Cr). Compared to sewage sludge, the potential contamination risk index of pyrolysis biochar obtained at 650℃ was reduced to 17.01, indicating a low ecological risk. The addition of 7% kaolin/zeolite further reduced the risk index of co-pyrolysis biochar prepared at 650℃ to 10.86/15.28. The characterization of biochar revealed that increase in the pyrolysis temperature and incorporation of additives are conducive to the formation of stable heavy metal-inorganics. This study demonstrates that the formation of stable mineral compounds containing heavy metals is the key to stabilizing heavy metals in pyrolysis biochar.     

生物炭施用对矿区污染农田土壤上油菜生长和重金属富集的影响

矿山的生产活动往往会造成周边农田的污染,而利用生物炭技术治理矿区周边污染农田土壤具有重要的现实意义。生物炭是指生物质在无氧或限氧条件下热裂解制备而成的一种细粒度、多孔性的环境友好型材料,其在调控温室气体排放,改良土壤性状,促进植物生长和控制环境污染物迁移转化方面应用潜力巨大。采用室内盆栽模拟实验,研究了不同水稻秸秆生物炭施用量（0、1%、5%）对郴州和龙岩地区矿山周边重金属污染的农田土壤的生化性状、油菜（Brassia campestris L.）产量、重金属累积和富集系数等的影响,为生物炭作为环境功能材料应用于矿山污染农田治理提供科学依据。结果表明：与对照相比,施加1%和5%生物炭均能提高土壤pH值和有机质质量分数,提升幅度随施用量的增加而升高,其中偏酸性的龙岩土壤的变化幅度更大;生物炭施用会影响土壤酶活性,5%生物炭处理下两种受试土壤中脲酶和过氧化物酶活性均显著提高,但酸性磷酸酶活性降低;龙岩土壤上的油菜产量在1%和5%生物炭施用处理下均显著提高,而郴州土壤上的油菜产量在1%生物炭处理下无显著变化,而在5%生物炭处理下降低了42.9%;生物炭施用影响了两种土壤上油菜可食部分重金属Cd、As和Pb的质量分数,但没有一致的规律;与对照相比,生物炭施用后郴州和龙岩土壤上油菜可食部分中Cd质量分数均出现下降趋势,但是仅5%生物炭处理的龙岩土壤具显著性差异;1%和5%生物炭施用处理使两种受试土壤上油菜可食部分Pb质量分数较对照处理显著降低（P〈0.05）,但降幅不同,郴州土壤降低了23.6%和22.0%,而偏酸性的龙岩土壤降低了82.1%和94.5%;生物炭施用后两种受试土壤上油菜可食部分As质量分数的变化不同,郴州土壤添加生物炭后油菜As质量分数呈上升趋势,且增量随生物炭施用量增加而升高,龙岩土壤则相反,1     

Decontamination of Cr(VI) facilitated formation of persistent free radicals on rice husk derived biochar

PFRs were produced on biochar during Cr(VI) decontamination. PFRs formation on biochar was owing to the oxidization of phenolic-OH by Cr(VI). Appearance of excessive oxidant led to the consumption of PFRs on biochar. Biochar charred at high temperature possessed great performance to Cr(VI) removal. This study investigated the facilitation of Cr(VI) decontamination to the formation of persistent free radicals (PFRs) on rice husk derived biochar. It was found that Cr(VI) remediation by biochar facilitated the production of PFRs, which increased with the concentration of treated Cr(VI). However, excessive Cr(VI) would induce their decay. Biochar with high pyrolysis temperature possessed great performance to Cr(VI) removal, which was mainly originated from its reduction by biochar from Inductively Coupled Plasma Optical Emission Spectroscopy and X-ray Photoelectron Spectroscopy. And the corresponding generation of PFRs on biochar was primarily ascribed to the oxidization of phenolic hydroxyl groups by Cr(VI) from Fourier Transform Infrared Spectroscopy analysis, which was further verified by the H₂O₂ treatment experiments. The findings of this study will help to illustrate the transformation of reactive functional groups on biochar and provide a new insight into the role of biochar in environmental remediation.     

Algal biomass derived biochar anode for efficient extracellular electron uptake from <Emphasis Type="Italic">Shewanella oneidensis</Emphasis> MR-1

The development of cost-effective and highly efficient anode materials for extracellular electron uptake is important to improve the electricity generation of bioelectrochemical systems. An effective approach to mitigate harmful algal bloom (HAB) is mechanical harvesting of algal biomass, thus subsequent processing for the collected algal biomass is desired. In this study, a low-cost biochar derived from algal biomass via pyrolysis was utilized as an anode material for efficient electron uptake. Electrochemical properties of the algal biochar and graphite plate electrodes were characterized in a bioelectrochemical system (BES). Compared with graphite plate electrode, the algal biochar electrode could effectively utilize both indirect and direct electron transfer pathways for current production, and showed stronger electrochemical response and better adsorption of redox mediators. The maximum current density of algal biochar anode was about 4.1 times higher than graphite plate anode in BES. This work provides an application potential for collected HAB to develop a cost-effective anode material for efficient extracellular electron uptake in BES and to achieve waste resource utilization.

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Machine learning and computational chemistry to improve biochar fertilizers: a review

Traditional fertilizers are highly inefficient, with a major loss of nutrients and associated pollution. Alternatively, biochar loaded with phosphorous is a sustainable fertilizer that improves soil structure, stores carbon in soils, and provides plant nutrients in the long run, yet most biochars are not optimal because mechanisms ruling biochar properties are poorly known. This issue can be solved by recent developments in machine learning and computational chemistry. Here we review phosphorus-loaded biochar with emphasis on computational chemistry, machine learning, organic acids, drawbacks of classical fertilizers, biochar production, phosphorus loading, and mechanisms of phosphorous release. Modeling techniques allow for deciphering the influence of individual variables on biochar, employing various supervised learning models tailored to different biochar types. Computational chemistry provides knowledge on factors that control phosphorus binding, e.g., the type of phosphorus compound, soil constituents, mineral surfaces, binding motifs, water, solution pH, and redox potential. Phosphorus release from biochar is controlled by coexisting anions, pH, adsorbent dosage, initial phosphorus concentration, and temperature. Pyrolysis temperatures below 600 °C enhance functional group retention, while temperatures below 450 °C increase plant-available phosphorus. Lower pH values promote phosphorus release, while higher pH values hinder it. Physical modifications, such as increasing surface area and pore volume, can maximize the adsorption capacity of phosphorus-loaded biochar. Furthermore, the type of organic acid affects phosphorus release, with low molecular weight organic acids being advantageous for soil utilization. Lastly, biochar-based fertilizers release nutrients 2–4 times slower than conventional fertilizers.

     

Adsorption of herring sperm DNA onto pine sawdust biochar: Thermodynamics and site energy distribution

● Adsorption of environmental deoxyribonucleic acid on biochar was studied. ● π−π interaction and electrostatic repulsion worked in the adsorption. ● Thermodynamics indicated the adsorption was spontaneous and endothermic. Environmental deoxyribonucleic acid (eDNA), which includes antibiotic resistance genes, is ubiquitous in the environment. The interactions between eDNA and biochar, a promising material widely used in soil amendment and water treatment, greatly affect the environmental behavior of eDNA. Hitherto few experimental evidences are available yet, especially on the information of thermodynamics and energy distribution to explains the interactions between biochar and eDNA. This study investigated the adsorption of herring sperm DNA (hsDNA) on pine sawdust biochar, with a specific emphasis on the adsorption thermodynamics and site energy distribution. The adsorption of hsDNA on biochar was enhanced by an increase in the pyrolysis and adsorption temperatures. The higher surface area, stronger π−π interaction, and weaker electrostatic repulsion between hsDNA and biochars prepared at high pyrolysis temperatures facilitated the adsorption of hsDNA. The thermodynamics indicated that the adsorption of hsDNA on biochar was spontaneous and endothermic. Therefore, higher temperature was beneficial for the adsorption of hsDNA on biochar; this was well explained by the increase in E^* and F(E^*) with the adsorption temperature. These results are useful for evaluating the migration and transformation of eDNA in the presence of biochar.     

Biochars derived from carp residues: characteristics and copper immobilization performance in water environments

● P-rich carp residues-derived biochars presented excellent Cu sorption capacity. ● Sorption mechanisms of Cu on CRBs were mainly precipitation and surface complexation. ● CRBs could immobilize Cu and reduce its bioavailability in aquatic environment. Heavy metal pollution has attracted worldwide attention because of its adverse impact on the aquatic environment and human health. The production of biochar from biowaste has become a promising strategy for managing animal carcasses and remediating heavy metal pollution in the aquatic environment. However, the sorption and remediation performance of carp residue-derived biochar (CRB) in Cu-polluted water is poorly understood. Herein, batches of CRB were prepared from carp residues at 450–650 °C (CRB450–650) to investigate their physicochemical characteristics and performance in the sorption and remediation of Cu-polluted water. Compared with a relatively low-temperature CRB (e.g., CRB450), the high-temperature biochar (CRB650) possessed a large surface area and thermodynamic stability. CRB650 contained higher oxygen-containing functional groups and P-associated minerals, such as hydroxyapatite. As the pyrolytic temperature increased from 450 to 650°C, the maximum sorption capacity of the CRBs increased from 26.5 to 62.5 mg/g. The adsorption process was a type of monolayer adsorption onto homogenous materials, and the sorption of Cu²⁺ on the CRB was mainly based on chemical adsorption. The most effective potential adsorption mechanisms were in order of electrostatic attraction and cation-π interaction > surface complexation and precipitation > pore-filling and cation exchange. Accordingly, the CRBs efficiently immobilized Cu²⁺ and reduced its bioavailability in water. These results provide a promising strategy to remediate heavy metal-polluted water using designer biochars derived from biowastes, particularly animal carcasses.     

Mechanism insight into the formation of H2S from thiophene pyrolysis: A theoretical study

• Possible formation pathways of H₂S were revealed in thiophene pyrolysis. • The influence of hydrogen radicals on thiophene pyrolysis was examined. • Thiophene decomposition starts with hydrogen transfer between adjacent C atoms. • The presence of hydrogen radicals significantly promotes the formation of H₂S. Pyrolysis is an efficient and economical method for the utilization of waste rubber, but the high sulfur content limits its industrial application. Currently, the migration and transformation of the element S during pyrolysis of waste rubber is far from well known. In this work, a density functional theory (DFT) method was employed to explore the possible formation pathways of H₂S and its precursors (radicals HS· and S·) during the pyrolysis of thiophene, which is an important primary pyrolytic product of rubber. In particular, the influence of reactive hydrogen radicals was carefully investigated in the thiophene pyrolysis process. The calculation results indicate that the decomposition of thiophene tends to be initiated by hydrogen transfer between adjacent carbon atoms, which needs to overcome an energy barrier of 312.4 kJ/mol. The optimal pathway to generate H₂S in thiophene pyrolysis involves initial H migration and S-C bond cleavage, with an overall energy barrier of 525.8 kJ/mol. In addition, a thiol intermediate that bears unsaturated C-C bonds is essential for thiophene pyrolysis to generate H₂S, which exists in multiple critical reaction pathways. Moreover, the presence of hydrogen radicals significantly changes the decomposition patterns and reduces the energy barriers for thiophene decomposition, thus promoting the formation of H₂S. The current work on H₂S formation from thiophene can provide some theoretical support to explore clean utilization technologies for waste rubber.     

人居生活废弃物生物黑炭对水溶液中Cd2+的吸附研究

以人居生活废弃物生物黑炭为材料,探讨生物黑炭对Cd2+的吸附动力学及热力学特性,通过平衡吸附法研究吸附时间、Cd2+初始质量浓度、吸附剂投加量、溶液pH值以及黑炭粒径对Cd2+吸附率的影响.结果表明,吸附时间为2h时基本达到吸附平衡,准二级动力学方程能很好地描述生物黑炭对Cd2+的吸附过程.Langmuir模型能较好地描述生物黑炭对Cd2+的等温吸附过程,根据该模型模拟得到25℃条件下Cd2+最大吸附量为6.22mg·g-1.Cd2+去除率随生物黑炭投加量的增加而增大;生物黑炭对Cd2+吸附量随其粒径减小而增大;溶液初始pH值为4.0～7.5时,pH值变化对Cd2+吸附量的影响不显著.采用人居生活废弃物生物黑炭去除水溶液中Cd2+时,控制溶液Cd2+初始质量浓度30mg·L-1,粒径小于0.25 mm,投加水平8g·L-1,反应温度25℃,反应时间1～2h,Cd2+去除率可达80％.人居生活废弃物生物黑炭可以作为去除污染水体中Cd2+的吸附剂.