Hydrocarbons

碳氢化合物
  • 文章类型: Journal Article
    调查了2019年和2022年在巴西东北海岸发生的事件中溢出的油的化学成分,以更好地了解其来源。和泄漏后的过程。这两个事件的油来自不同的来源,根据他们的指纹,碳氢化合物成分和特定的生物标志物,如C23三环terpane和齐墩果烷。尽管存在差异,烃源岩在古环境和沉积条件上有相似之处,两种油几乎没有风化,主要是由于蒸发和溶解。我们对2019年溢油的发现加强了它是一种混合产品,富含较轻的正构烷烃和25-norhopane。不同的是,2022年的样品显示出非加工原油的特征,该原油来自储罐中的石蜡矿床。报告的这些溢油事件样品的分子组成和诊断比率有助于建立基线,以持续监测海洋生态系统中的溢油。
    The chemical composition of spilt oils from events that took place on the north-eastern coast of Brazil in 2019 and 2022 was investigated to better understand their sources, and post-spill processes. Oils from both events originated from different sources, based on their fingerprints, hydrocarbons composition and specific biomarkers, such as the C23 tricyclic terpane and oleanane. Despite the differences, the source rocks share similarities in paleoenvironments and depositional conditions and both oils suffered little weathering, mainly due to evaporation and dissolution. Our findings for 2019 spilt oil reinforce that it is a mixed product, enriched both in lighter n-alkanes and 25-norhopanes. Differently, the 2022 samples exhibited characteristics of a non-processed crude oil that originated from a paraffinic deposit in storage tanks. The molecular composition and diagnostic ratios reported for samples from these spill events help to establish baselines for ongoing monitoring of oil spills in marine ecosystems.
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  • 文章类型: Journal Article
    对两种不同的炼油厂含油污泥(ROS)样品进行催化共热解以促进资源回收。在500至600°C的温度范围内进行非催化热解以确定高油收率。较高的温度将油的产量提高到〜24wt%,而S1的焦炭形成保持不变(~45%)。相反,S2表现出比S1显著更低的油产率(~4wt%)。S1的热解油由酚类(在600°C时为〜50%)组成,而S2油中占主导地位(在600°C时为〜80%)。S1的催化热解对油产率没有实质性影响,但油组成显着变化。高碳氢化合物,酚类物质,用分子筛(MS)获得芳烃,金属渣,和ZSM-5。在MS存在下,S2与木屑(SD)的催化共热解提高了油产率,并且所得的油由高烃(~54%)和芳烃(~44%)组成。
    Catalytic co-pyrolysis of two different refinery oily sludge (ROS) samples was conducted to facilitate resource recovery. Non-catalytic pyrolysis in temperatures ranging from 500 to 600°C was performed to determine high oil yields. Higher temperatures enhanced the oil yields up to ~ 24 wt%, while char formation remained unchanged (~ 45%) for S1. Conversely, S2 exhibited a notably lower oil yield (~ 4 wt%) than S1. Pyrolysis oil of S1 consisted of phenolics (~ 50% at 600 °C) whereas hydrocarbons were predominant in S2 oil (~ 80% at 600 °C). Catalytic pyrolysis of S1 did not exhibit a substantial impact on oil yields but the oil composition varied significantly. High hydrocarbons, phenolics, and aromatics were obtained with molecular sieve (MS), metal slag, and ZSM-5, respectively. Catalytic co-pyrolysis of S2 with sawdust (SD) in the presence of MS enhanced the oil yield, and the resulting oil consisted of high hydrocarbons (~ 54%) and aromatics (~ 44%).
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  • 文章类型: Journal Article
    背景:通过利用植物进行植物修复的应用已用于控制水域中的石油污染。风信子是可以作为植物修复剂的植物之一,因为这种植物可以减少包括石油碳氢化合物在内的各种污染物。本研究旨在研究不同浓度下石油烃的还原能力,包括改善水质。方法:本研究由一种处理(石油烃)组成,由五个因素组成,重复三个。处理包括10ppm(E1),30ppm(E2),50ppm(E3),70ppm(E4),90ppm(E5),和(E0),没有水生植物作为对照。每天观察治疗,并从第一天开始测量(D-1),第七天(D-7)第14天(D-14)。还测量了每种处理的水质,如水温,pH值,和溶解氧。结果:结果表明,风信子植物能够将总石油烃(TPH)中的碳氢化合物减少79%,而没有风信子的自然含量仅为17-27%。水中TPH的减少与风信子叶片中叶绿素的减少是一致的,其次是水介质中溶解氧的增加。结论:总之,风信子可以减少石油碳氢化合物,它们也可以改善水质。
    Background: The application of phytoremediation by utilizing plants has been used to control oil pollution in waters. One of the plants that can act as a phytoremediator is the hyacinth because this plant can reduce various pollutants including petroleum hydrocarbons. This study aims to study the reduction ability of petroleum hydrocarbons at different concentrations including improving water quality. Methods: This study consisted of one treatment (petroleum hydrocarbon) consisting of five factors with three replicates. The treatments consisted of 10 ppm (E1), 30 ppm (E2), 50 ppm (E3), 70 ppm (E4), 90 ppm (E5), and (E0) without aquatic plants as controls. The treatments were observed daily and measured from the first day (D-1), the seventh day (D-7), and the 14 th day (D-14). The water quality in each treatment was also measured, such as water temperature, pH, and dissolved oxygen. Results: The results showed that the hyacinth plant was able to reduce hydrocarbon in terms of total petroleum hydrocarbon (TPH) by 79% while it was only between 17-27% naturally without the hyacinth. The reduction of TPH in the water was in line with the decrease of chlorophyll in the leaves of hyacinths, and it was followed by the increase of dissolved oxygen in the water media. Conclusions: In conclusion, hyacinths can reduce petroleum hydrocarbons and they can improve the water quality as well.
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  • 文章类型: Journal Article
    海洋石油污染对环境和生物体的健康有很大影响。生物修复清洁策略是解决此问题的有希望的环保替代方案。以前,我们设计并报道了由四种海洋菌株组成的碳氢化合物(HC)降解微生物联盟,这些菌株属于Alloalcanivoraxxenomutans,aestusnigri假单胞菌,Paenacartactersp.,还有铜绿假单胞菌.然而,关于这种细菌财团用于HC生物修复的代谢潜力的知识尚未得到很好的了解。这里,我们分析了这些海洋细菌菌株的完整基因组,并进行了系统发育重建以及138个细菌菌株。同一物种或属的完整基因组之间的合成,揭示了同一物种菌株之间的高度保守性,覆盖超过91%的基因组序列。功能预测强调了与HC降解相关的大量基因,这可能会导致联盟内部的功能冗余;然而,在四个基因组中发现了与芳香降解相关的独特和完整的基因簇,建议底物专业化。涉及HC降解的基因的Pangenome增益和损失分析提供了对这些能力的进化史的见解,阐明与烷烃和芳烃降解相关基因的获取和丢失。我们的工作,包括比较基因组分析,次级代谢产物的鉴定,和HC降解基因的预测,增强了我们对这些海洋细菌在原油污染的海洋环境中的功能多样性和生态作用的理解,并有助于生物修复的应用知识。
    Ocean oil pollution has a large impact on the environment and the health of living organisms. Bioremediation cleaning strategies are promising eco-friendly alternatives for tackling this problem. Previously, we designed and reported a hydrocarbon (HC) degrading microbial consortium of four marine strains belonging to the species Alloalcanivorax xenomutans, Halopseudomonas aestusnigri, Paenarthrobacter sp., and Pseudomonas aeruginosa. However, the knowledge about the metabolic potential of this bacterial consortium for HC bioremediation is not yet well understood. Here, we analyzed the complete genomes of these marine bacterial strains accompanied by a phylogenetic reconstruction along with 138 bacterial strains. Synteny between complete genomes of the same species or genus, revealed high conservation among strains of the same species, covering over 91% of their genomic sequences. Functional predictions highlighted a high abundance of genes related to HC degradation, which may result in functional redundancy within the consortium; however, unique and complete gene clusters linked to aromatic degradation were found in the four genomes, suggesting substrate specialization. Pangenome gain and loss analysis of genes involved in HC degradation provided insights into the evolutionary history of these capabilities, shedding light on the acquisition and loss of relevant genes related to alkane and aromatic degradation. Our work, including comparative genomic analyses, identification of secondary metabolites, and prediction of HC-degrading genes, enhances our understanding of the functional diversity and ecological roles of these marine bacteria in crude oil-contaminated marine environments and contributes to the applied knowledge of bioremediation.
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  • 文章类型: Journal Article
    在大气压化学电离质谱(APCI-MS)中,[M-3H+H2O]+离子可递送分析物特异性信号,其使得能够直接分析挥发性正烷烃混合物。潜在的电离机制一直是公开辩论的主题,特别是当湿度水平随时间变化时,水的作用不够明确,无法进行可靠的过程分析。这可能是个问题,特别是在在线监控中,其中分析物积聚在离子源中也可能发生。这里,我们通过将样品注射的载气从干燥状态更改为润湿状态以及使用18O标记的水来研究水在挥发性正构烷烃的APCI-MS中的作用。这允许区分气态和表面吸附的水分子。虽然吸附水似乎是通过与分析物分子的表面反应产生所需[M-3H+H2O]+信号的原因,发现气态水可以促进不同(不依赖分析物的)碳氢化合物的CnH2n1O形成,揭示了在连续操作期间与离子源中积累的烃物质的反应。同时,气态水与分析物分子竞争电离,从而抑制了烷基(CnH2n1)和烯基(CnH2n-1)离子的形成。结果表明,由于碳氢化合物的吸附,记忆效应,当电离室经历突然的湿度变化时,这可能会导致严重的解释困难。通过不断保持高湿度并因此稳定电离条件,可以促进在烷烃/水混合物中使用[M-3HH2O]进行正构烷烃分析。
    In atmospheric pressure chemical ionization mass spectrometry (APCI-MS), [M-3H+H2O]+ ions can deliver analyte-specific signals that enable direct analysis of volatile n-alkane mixtures. The underlying ionization mechanisms have been the subject of open debate, and in particular the role of water is insufficiently clarified to allow for reliable process analytics when the humidity level changes over time. This can be a problem, particularly in online monitoring, where analyte accumulation in the ion source can also occur. Here, we investigated the role of water during APCI-MS of volatile n-alkanes by changing the carrier gas for sample injection from a dry to a wetted state as well as by using 18O-labeled water. This allowed for a distinction between gaseous and surface-adsorbed water molecules. While adsorbed water seems to be responsible for the desired [M-3H+H2O]+ signals through surface reactions with the analyte molecules, gaseous water was found to promote the formation of CnH2n+1O+ of different (and analyte-independent) hydrocarbons, revealing a reaction with hydrocarbon species which accumulated in the ion source during continuous operation. At the same time, gaseous water competed with analyte molecules for ionization and thus suppressed the formation of alkyl (CnH2n+1+) and alkenyl (CnH2n-1+) ions. The results reveal a memory effect due to hydrocarbon adsorption, which may cause severe interpretation difficulties when the ionization chamber undergoes sudden humidity changes. The use of [M-3H+H2O]+ for n-alkane analysis in alkane/water mixtures can be facilitated by constantly maintaining high humidity and hence stabilizing the ionization conditions.
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  • 文章类型: Journal Article
    可溶性磷(P)缺乏和石油烃污染都是土壤环境中的挑战。虽然溶解磷酸盐的细菌和降解碳氢化合物的细菌已被鉴定并用于环境生物修复,这种细菌与可溶性磷缺乏和碳氢化合物污染共同适应的报道很少。本研究探讨了oleivoransS4(A.oleivoransS4)使用正十六烷(H)溶解磷酸盐,葡萄糖(G),和在磷酸三钙(TCP)培养基中的混合碳源(HG)。A.oleivoransS4在H-TCP中表现出强劲的增长,释放31mgL-1的可溶性P.A.oleivoransS4在G-TCP中几乎没有增长,释放654mgL-1的可溶性P.在HG-TCP中,生物量超过了H-TCP,磷酸盐释放量与G-TCP相当。HPLC分析显示H-TCP中存在少量TCA循环酸,G-TCP和HG-TCP中存在大量葡糖酸盐。转录组学分析显示与烷烃降解相关的基因表达升高,P饥饿,N利用率,和在H-TCP中合成海藻糖,揭示了A.oleivoransS4的分子共适应机制。此外,葡萄糖的加入增强了烷烃的降解,P和N利用率,和减少海藻糖合成。这表明不完全的葡萄糖代谢可能为其他反应提供能量,葡萄糖酸盐介导的可溶性P的增加可能减轻氧化应激。总的来说,A.oleivoransS4被证明有希望修复可溶性P缺乏和碳氢化合物污染的环境,和葡萄糖刺激其转化为超磷酸盐溶解细菌。
    Both soluble phosphorus (P) deficiency and petroleum hydrocarbon contamination represent challenges in soil environments. While phosphate-solubilizing bacteria and hydrocarbon-degrading bacteria have been identified and employed in environmental bioremediation, the bacteria co-adapted to soluble P deficiency and hydrocarbon contamination has rarely been reported. This study explored the ability of Acinetobacter oleivorans S4 (A. oleivorans S4) to solubilize phosphate using n-hexadecane (H), glucose (G), and a mixed carbon source (HG) in tricalcium phosphate (TCP) medium. A. oleivorans S4 exhibited robust growth in H-TCP, releasing 31 mg L-1 of soluble P. Conversely, A. oleivorans S4 barely grew in G-TCP, releasing 654 mg L-1 of soluble P. In HG-TCP, biomass surpassed that in H-TCP, with phosphate release comparable to that in G-TCP. HPLC analysis revealed a small amount of TCA cycle acids in H-TCP and a large amount of gluconate in G-TCP and HG-TCP. Transcriptomic analysis showed elevated expression of genes associated with alkane degradation, P starvation, N utilization, and trehalose synthesis in H-TCP, revealing the molecular co-adaptation mechanism of A. oleivorans S4. Furthermore, the addition of glucose enhanced alkane degradation, P and N utilization, and reduced trehalose synthesis. It indicated that incomplete glucose metabolism may provide energy for other reactions, and the increase in soluble P mediated by gluconate may alleviate oxidative stress. Overall, A. oleivorans S4 proves promising for remediating soluble P-deficient and hydrocarbon-contaminated environments, and glucose stimulates its transformation into a super phosphate-solubilizing bacterium.
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  • 文章类型: Journal Article
    使用石墨氮化碳(g-C3N4)聚合物将CO2选择性光催化还原为高价值烃具有重要的现实意义。在这里,成功构建了具有高局部电子密度位点的氰基官能化g-C3N4(CN-g-C3N4),用于将CO2选择性光还原为CH4和C2H4。其中有效的吸电子氰基在CN-g-C3N4中诱导巨大的内部电场,显着促进光生电子的定向迁移并将其集中在附近。因此,在其氰基周围产生了一个高局部电子密度位点。此外,这种结构还可以有效地促进CO2的吸附和活化,同时牢固地锚定*CO中间体,促进其随后的氢化和偶联反应。因此,使用H2O作为还原剂,CN-g-C3N4实现了高效和选择性的光催化CO2还原为CH4和C2H4的活性,最大速率分别为6.64和1.35µmolg-1h-1,比g-C3N4和g-C3N4纳米片高出69.3和53.8倍。总之,这项工作说明了构建具有高局部电子密度的还原位点对于有效和选择性地将CO2光还原为碳氢化合物的重要性。
    Selective photocatalytic CO2 reduction to high-value hydrocarbons using graphitic carbon nitride (g-C3N4) polymer holds great practical significance. Herein, the cyano-functionalized g-C3N4 (CN-g-C3N4) with a high local electron density site is successfully constructed for selective CO2 photoreduction to CH4 and C2H4. Wherein the potent electron-withdrawing cyano group induces a giant internal electric field in CN-g-C3N4, significantly boosting the directional migration of photogenerated electrons and concentrating them nearby. Thereby, a high local electron density site around its cyano group is created. Moreover, this structure can also effectively promote the adsorption and activation of CO2 while firmly anchoring *CO intermediates, facilitating their subsequent hydrogenation and coupling reactions. Consequently, using H2O as a reducing agent, CN-g-C3N4 achieves efficient and selective photocatalytic CO2 reduction to CH4 and C2H4 activity, with maximum rates of 6.64 and 1.35 µmol g-1 h-1, respectively, 69.3 and 53.8 times higher than bulk g-C3N4 and g-C3N4 nanosheets. In short, this work illustrates the importance of constructing a reduction site with high local electron density for efficient and selective CO2 photoreduction to hydrocarbons.
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  • 文章类型: Journal Article
    Khuzestan省(伊朗西南部)的石油工业是造成该地区环境污染的主要原因之一。TPH,包括芳族和脂族化合物,是造成污染的重要参数。本研究旨在调查2022年阿瓦兹油田TPH污染土壤的来源。土壤样本是从四个石油中心(一个石油开采单位,一个石油脱盐装置,石油钻井平台,和一个泵油中心)。油田外的区域被确定为控制区。根据标准方法从每个区域取10个样品,重复三次。通过HPLC和GC方法测量芳香族和脂肪族化合物。正矩阵分解(PMF)模型和异构体比率用于确定土壤样品中芳香族化合物的来源分配。还使用影响范围低和影响范围中值指数来评估土壤样品中石油化合物的生态风险水平。结果表明,在阿瓦兹油田的土壤样品中,苯并氟蒽的浓度最高,平均为5667.7ug/kg。在来自泵油中心区域的样品中发现最高的平均值为7329.48ug/kg,而最低的是在对照样品中发现的19.4ug/kg-1。在泵油中心也发现了最高水平的脂肪族成分,共3649(mg。kg-1)。土壤样品中石油化合物的来源解析结果表明,石油活性占土壤中多环芳烃含量的51.5%。38.3%的其他测量化合物具有人为起源,这些化合物中只有10.1%是生物来源的。异构比的结果还表明了PAH化合物的局部石油和热解起源,这与PMF结果一致。对环境中PAHs释放产生的生态风险指数的分析表明,除了荧蒽,石油开采单位区域的其他PAHs高于影响范围中位数(ERM),并且处于高风险。研究结果表明,土壤总石油烃(TPH)污染,芳香族和脂肪族,处于高水平,主要是由人类活动引起的,特别是石油活动。
    The oil industry in Khuzestan province (Southwest Iran) is one of the main reasons contributing to the pollution of the environment in this area. TPH, including both aromatic and aliphatic compounds, are important parameters in creating pollution. The present study aimed to investigate the source of soil contamination by TPH in the Ahvaz oil field in 2022. The soil samples were collected from four oil centers (an oil exploitation unit, an oil desalination unit, an oil rig, and a pump oil center). An area outside the oil field was determined as a control area. Ten samples with three replicates were taken from each area according to the standard methods. Aromatic and aliphatic compounds were measured by HPLC and GC methods. The positive matrix factorization (PMF) model and isomeric ratios were used to determine the source apportionment of aromatic compounds in soil samples. The effects range low and effects range median indices were also used to assess the level of ecological risk of petroleum compounds in the soil samples. The results showed that Benzo.b.fluoranthene had the highest concentration with an average of 5667.7 ug/kg in soil samples in the Ahvaz oil field. The highest average was found in samples from the pump oil center area at 7329.48 ug/kg, while the lowest was found in control samples at 1919.4 ug/kg-1. The highest level of aliphatic components was also found in the pump oil center, with a total of 3649 (mg. Kg-1). The results of source apportionment of petroleum compounds in soil samples showed that oil activities accounted for 51.5% of the measured PAHs in soil. 38.3% of other measured compounds had anthropogenic origins, and only 10.1% of these compounds were of biotic origin. The results of the isomeric ratios also indicated the local petroleum and pyrogenic origin of PAH compounds, which is consistent with the PMF results. The analysis of ecological risk indices resulting from the release of PAHs in the environment showed that, except for fluoranthene, other PAHs in the oil exploitation unit area were above the effects range median level (ERM) and at high risk. The results of the study showed that soil pollution by total petroleum hydrocarbons (TPH), both aromatic and aliphatic, is at a high level, and is mainly caused by human activities, particularly oil activities.
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  • 文章类型: Journal Article
    碳氢化合物燃料每单位质量的能量大约是商用电池的50倍,因此,即使将碳氢燃料中包含的能量的10%转化为电能,也可以提供比电池更具质量效率的电能来源。考虑到碳氢化合物燃料与氢气相比的可储存性,研究了直接烃类聚合物电解质膜燃料电池的可行性。使用极纯(>99.99%)丙烷,电池开路电压(OCV)仅为0.05V,产生的功率可忽略不计。然而,添加痕量的不饱和烃,电池的OCV为0.85V,产生的功率,甚至在不饱和烃添加停止之后。在足够高的电流密度下,功率输出逐渐下降,然后电池迅速“熄灭”,但通过在短时间间隔内定期关闭电流,平均功率密度可以显着增加。化学分析表明,流出物中不存在显著量的烃中间体或CO,并且烃燃料向CO2和H2O的转化几乎完成。开发了一种分析模型,该模型结合了活性阳极催化剂位点转化为非活性位点的相对速率,反之亦然,以解释这种行为。模型预测与实验观察结果一致;讨论了可能的物理机制。
    Hydrocarbon fuels contain approximately 50 times more energy per unit mass than commercial batteries, thus converting even 10% of the energy contained in hydrocarbon fuels to electrical energy could present a more mass-efficient electrical energy source than batteries. Considering the storability of hydrocarbon fuels compared to hydrogen, the viability of direct hydrocarbon polymer electrolyte membrane fuel cells was examined. With extremely pure (> 99.99%) propane, the cell Open-Circuit Voltage (OCV) was only 0.05 V and produced negligible power. However, with addition of trace quantities of unsaturated hydrocarbons, the cell had an OCV of 0.85 V and produced power, even after the unsaturated hydrocarbon addition was discontinued. At sufficiently high current densities, power output gradually decreased then the cell rapidly \"extinguished\" but by periodically shutting off the current for short time intervals the average power density could be increased significantly. Chemical analysis revealed that no significant amounts of hydrocarbon intermediates or CO were present in the effluent and that conversion of the hydrocarbon fuel to CO2 and H2O was nearly complete. An analytical model incorporating the relative rates of conversion of active anode catalyst sites to inactive sites and vice versa was developed to interpret this behavior. The model predictions were consistent with the experimental observations; possible physical mechanisms are discussed.
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  • 文章类型: Journal Article
    聚乙烯和聚丙烯等聚烯烃是全球生产最多的塑料废物,然而,由于它们的不活泼,很难转化为有用的产品。热解是大规模处理混合的一种实用方法,受污染的塑料,允许它们转化为工业相关的石化产品。金属有机骨架(MOFs),尽管它们在多相催化中具有巨大的效用,由于其感知的热不稳定性以及聚乙烯和聚丙烯不能渗透其孔,聚烯烃解聚已被忽略。在这里,我们证明了含有配位不饱和氧化锆节点的UiO-66MOFs的可行性,作为有效的热解催化剂,显着提高有价值的液态和气态烃的产率,同时将产生的残余固体的量减半。反应发生在路易斯酸性UiO-66氧化锆节点上,不需要贵金属,并产生与沸石催化产生的富含芳烃的烃明显不同的脂肪族产物分布。我们还证明了在热解温度下聚烯烃渗透到UiO-66孔中的第一个明确表征,允许进入MOF内部丰富的Zr-oxo节点以进行有效的C-C裂解。我们的工作强调了MOFs作为高度可设计的非均相催化剂用于塑料解聚的潜力,可以在反应性方面补充常规催化剂。
    Polyolefins such as polyethylenes and polypropylenes are the most-produced plastic waste globally, yet are difficult to convert into useful products due to their unreactivity. Pyrolysis is a practical method for large-scale treatment of mixed, contaminated plastic, allowing for their conversion into industrially-relevant petrochemicals. Metal-organic frameworks (MOFs), despite their tremendous utility in heterogenous catalysis, have been overlooked for polyolefin depolymerization due to their perceived thermal instabilities and inability of polyethylenes and polypropylenes to penetrate their pores. Herein, we demonstrate the viability of UiO-66 MOFs containing coordinatively-unsaturated zirconia nodes, as effective catalysts for pyrolysis that significantly enhances the yields of valuable liquid and gas hydrocarbons, whilst halving the amounts of residual solids produced. Reactions occur on the Lewis-acidic UiO-66 zirconia nodes, without the need for noble metals, and yields aliphatic product distributions distinctly different from the aromatic-rich hydrocarbons from zeolite catalysis. We also demonstrate the first unambiguous characterization of polyolefin penetration into UiO-66 pores at pyrolytic temperatures, allowing access to the abundant Zr-oxo nodes within the MOF interior for efficient C-C cleavage. Our work highlights the potential of MOFs as highly-designable heterogeneous catalysts for depolymerization of plastics which can complement conventional catalysts in reactivity.
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