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Redox Active Organic-Carbon Composites for Capacitive Electrodes: A Review 电容电极氧化还原活性有机碳复合材料研究进展
Pub Date : 2021-07-28 DOI: 10.3390/suschem2030024
J. N’Diaye, Raunaq Bagchi, J. Howe, K. Lian
The pressing concerns of environmental sustainability and growing needs of clean energy have raised the demands of carbon and organic based energy storage materials to a higher level. Redox-active organic-carbon composites electrodes are emerging to be enablers for high-performance, high power and long-lasting energy storage solutions, especially for electrochemical capacitors (EC). This review discusses the electrochemical redox active organic compounds and their composites with various carbonaceous materials focusing on capacitive performance. Starting with the most common conducting polymers, we expand the scope to other emerging redox active molecules, compounds and polymers as well as common carbonaceous substrates in composite electrodes, including graphene, carbon nanotube and activated carbon. We then discuss the first-principles computational studies pertaining to the interactions between the components in the composites. The fabrication methodologies for the composites with thin organic coatings are presented with their merits and shortcomings. The capacitive performances and features of the redox active organic-carbon composite electrodes are then summarized. Finally, we offer some perspectives and future directions to achieve a fundamental understanding and to better design organic-carbon composite electrodes for ECs.
对环境可持续性的迫切关注和对清洁能源日益增长的需求,将碳基和有机基储能材料的需求提高到一个更高的水平。氧化还原活性有机碳复合材料电极正在成为高性能、高功率和持久储能解决方案的推动因素,特别是对于电化学电容器(EC)。本文综述了电化学氧化还原活性有机化合物及其与各种碳质材料的复合材料的电容性能。从最常见的导电聚合物开始,我们将范围扩展到其他新兴的氧化还原活性分子,化合物和聚合物以及复合电极中常见的碳质衬底,包括石墨烯,碳纳米管和活性炭。然后我们讨论了有关复合材料中组件之间相互作用的第一性原理计算研究。介绍了薄有机涂层复合材料的制备方法及其优缺点。综述了氧化还原活性有机碳复合电极的电容性能和特点。最后,我们提出了一些观点和未来的发展方向,以实现对有机碳复合材料电极的基本理解和更好的设计。
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引用次数: 6
Greenness Assessment and Synthesis for the Bio-Based Production of the Solvent 2,2,5,5-Tetramethyloxolane (TMO) 生物基溶剂2,2,5,5-四甲基氧烷(TMO)的绿色评价与合成
Pub Date : 2021-07-28 DOI: 10.3390/suschem2030023
Fergal P Byrne, J. Clark, C. Angelici, E. de Jong, T. Farmer
2,2,5,5-tetramethyloxolane (TMO) has recently been identified and demonstrated as a safer solvent to replace toluene, THF, and hydrocarbons in a handful of applications. Herein, several bio-based routes to TMO are presented and assessed for greenness, assisted by the CHEM21 Metrics Toolkit and BioLogicTool plots. Using glucose as a common starting point, two chemocatalytic routes and two biochemical routes to TMO were identified and the pathways compared using the aforementioned tools. In addition, bio-based TMO was synthesised via one of these routes; from methyl levulinate supplied by Avantium, a by-product of the sugar dehydration step during the production of 2,5-furandicarboxylic acid. First, methyl levulinate underwent triple methylation using methyl magnesium chloride (MeMgCl) to yield 2,5-dimethylhexane-2,5-diol (DHL) in high yields of 89.7%. Then DHL was converted to high purity TMO (>98.5%) by cyclodehydration using H-BEA zeolites based on the previously reported approach. Bio-based content of this TMO was confirmed by ASTM D6866-20 Method B and found to have 64% bio-based carbon, well above the threshold of 25% set by CEN/TC 411 standards and matching the anticipated content. This study represents the first demonstration of a bio-based synthesis of TMO and confirmation of bio-content by accepted standards.
2,2,5,5-四甲基氧烷(TMO)最近被确定并证明是一种更安全的溶剂,可以在少数应用中取代甲苯、四氢呋喃和碳氢化合物。本文提出了几种基于生物的TMO途径,并在CHEM21 Metrics Toolkit和BioLogicTool绘图的协助下评估了其绿色度。以葡萄糖为共同起点,确定了TMO的两种化学催化途径和两种生化途径,并使用上述工具对途径进行了比较。此外,生物基TMO通过其中一种途径合成;从Avantium提供的乙酰丙酸甲酯中提取,这是生产2,5-呋喃二羧酸过程中糖脱水步骤的副产物。首先,用甲基氯化镁(MeMgCl)对乙酰丙酸甲酯进行三甲基化,以89.7%的高收率得到2,5-二甲基己烷-2,5-二醇(DHL)。然后根据之前报道的方法,用H-BEA沸石环脱水将DHL转化为高纯度的TMO(>98.5%)。该TMO的生物基含量经ASTM D6866-20方法B确认,发现生物基碳含量为64%,远高于CEN/TC 411标准设定的25%的阈值,符合预期含量。这项研究首次展示了生物基合成TMO,并通过公认的标准确认了其生物含量。
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引用次数: 5
Removing Simultaneously Sulfur and Nitrogen from Fuel under a Sustainable Oxidative Catalytic System 可持续氧化催化系统同时脱除燃料中的硫和氮
Pub Date : 2021-06-19 DOI: 10.3390/suschem2020022
Dinis F. Silva, Alexandre M. Viana, F. Mirante, B. de Castro, L. Cunha-Silva, Salete S. Balula
An effective process to remove nitrogen-based compounds from fossil fuels without harming the process of sulfur removal is an actual gap in refineries. A success combination of desulfurization and denitrogenation processes capable of completely removing the most environmental contaminates in diesel under sustainable conditions was achieved in this work, applying polyoxometalates as catalysts, hydrogen peroxide as oxidant, and an immiscible ionic liquid as an extraction solvent. The developed process based in simultaneous oxidative desulfurization (ODS) and oxidative denitrogenation (ODN) involved initial extraction of sulfur and nitrogen compounds followed by catalytic oxidation. Keggin-type polyoxomolybdates revealed much higher reusing capacity than the related polyoxotungstate. Effectively, the first catalysts practically allowed complete sulfur and nitrogen removal only in 1 h of reaction and for ten consecutive cycles, maintaining the original catalyst and ionic liquid samples.
从化石燃料中去除氮基化合物而不损害硫去除过程的有效工艺是炼油厂的实际空白。在这项工作中,采用多金属氧酸盐作为催化剂,过氧化氢作为氧化剂,非混溶离子液体作为萃取溶剂,成功地实现了脱硫和脱氮工艺的结合,能够在可持续条件下完全去除柴油中的大多数环境污染物。基于同时氧化脱硫(ODS)和氧化脱氮(ODN)的工艺是先提取硫和氮化合物,然后进行催化氧化。keggin型多氧钼酸盐比相关的多氧钨酸盐具有更高的重复利用能力。实际上,第一批催化剂实际上只允许在1小时的反应和连续10个循环中完全去除硫和氮,保持了原始催化剂和离子液体样品。
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引用次数: 5
Environmental Contamination and Human Exposure to Select Endocrine-Disrupting Chemicals: A Review 环境污染与人类暴露于某些内分泌干扰化学物质:综述
Pub Date : 2021-05-31 DOI: 10.3390/SUSCHEM2020020
S. Sangeetha, K. Vimalkumar, B. Loganathan
Endocrine-disrupting compounds (EDCs) are exogenous compounds that interfere with the normal hormone functions and ultimately lead to health disorders. Parabens, phenols, and phthalates are well-known EDCs, produced globally in large quantities and widely used in a variety of applications. Several studies have monitored these compounds in a variety of environmental matrices, including air, water, sediment, fish, human tissues, soil, indoor dust, and biosolids, etc. In recent years, environmental contamination and human exposure to these chemicals have become a great concern, due to their residue levels exceeding the permissible/acceptable limits. In this review, we focus on the origin of these EDCs, aquatic contamination pathways, distribution, human exposure, health implications, and healthcare costs. Further, this review identifies critical challenges and future research needs in removing or minimizing environmental contamination and exposure to these chemicals to protect living resources.
内分泌干扰化合物(EDCs)是干扰正常激素功能并最终导致健康失调的外源性化合物。对羟基苯甲酸酯、苯酚和邻苯二甲酸酯是众所周知的EDCs,在全球大量生产并广泛用于各种应用。一些研究监测了这些化合物在各种环境基质中的情况,包括空气、水、沉积物、鱼、人体组织、土壤、室内灰尘和生物固体等。近年来,由于这些化学物质的残留水平超过了允许/可接受的限度,环境污染和人类接触这些化学物质已成为人们非常关注的问题。在这篇综述中,我们将重点介绍这些EDCs的来源、水生污染途径、分布、人类暴露、健康影响和医疗成本。此外,本综述确定了消除或尽量减少环境污染和暴露于这些化学物质以保护生物资源的关键挑战和未来的研究需要。
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引用次数: 17
Longevity of Raw and Lyophilized Crude Urease Extracts 生的和冻干的粗脲酶提取物的寿命
Pub Date : 2021-05-06 DOI: 10.3390/SUSCHEM2020018
N. Javadi, H. Khodadadi Tirkolaei, N. Hamdan, E. Kavazanjian
The stability (longevity of activity) of three crude urease extracts was evaluated in a laboratory study as part of an effort to reduce the cost of urease for applications that do not require high purity enzyme. A low-cost, stable source of urease will greatly facilitate engineering applications of urease such as biocementation of soil. Inexpensive crude extracts of urease have been shown to be effective at hydrolyzing urea for carbonate precipitation. However, some studies have suggested that the activity of a crude extract may decrease with time, limiting the potential for its mass production for commercial applications. The stability of crude urease extracts shown to be effective for biocementation was studied. The crude extracts were obtained from jack beans via a simple extraction process, stored at room temperature and at 4 ℃, and periodically tested to evaluate their stability. To facilitate storage and transportation of the extracted enzyme, the longevity of the enzyme following freeze drying (lyophilization) to reduce the crude extract to a powder and subsequent re-hydration into an aqueous solution was evaluated. In an attempt to improve the shelf life of the lyophilized extract, dextran and sucrose were added during lyophilization. The stability of purified commercial urease following rehydration was also investigated. Results of the laboratory tests showed that the lyophilized crude extract maintained its activity during storage more effectively than either the crude extract solution or the rehydrated commercial urease. While incorporating 2% dextran (w/v) prior to lyophilization of the crude extract increased the overall enzymatic activity, it did not enhance the stability of the urease during storage.
在实验室研究中评估了三种粗脲酶提取物的稳定性(活性寿命),作为降低脲酶成本的一部分,用于不需要高纯度酶的应用。低成本、稳定的脲酶来源将极大地促进脲酶在土壤生物固结等工程上的应用。廉价的尿素酶粗提取物已被证明是有效的水解尿素碳酸盐沉淀。然而,一些研究表明,粗提取物的活性可能会随着时间的推移而降低,这限制了其大规模生产用于商业应用的潜力。研究了脲酶粗提物对生物胶凝效果较好的稳定性。采用简单的提取工艺提取豆角粗提物,分别在室温和4℃条件下保存,并定期检测其稳定性。为了便于提取的酶的储存和运输,对酶在冷冻干燥(冻干)后的寿命进行了评估,以将粗提取物还原为粉末,然后再水化成水溶液。为了提高冻干提取物的保质期,在冻干过程中加入葡聚糖和蔗糖。还研究了纯化的商业脲酶复水后的稳定性。实验室试验结果表明,冻干粗提物在贮存期间比粗提物溶液或复水合商业脲酶更有效地保持其活性。虽然在粗提取物冻干前加入2%葡聚糖(w/v)可以提高酶的总活性,但在储存过程中并没有提高脲酶的稳定性。
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引用次数: 7
Continuous Valorization of Glycerol into Solketal: Recent Advances on Catalysts, Processes, and Industrial Perspectives 甘油连续增值成索酮:催化剂、工艺和工业前景的最新进展
Pub Date : 2021-04-21 DOI: 10.3390/SUSCHEM2020017
Isabella Corrêa, R. Faria, A. Rodrigues
With the global biodiesel production growing as never seen before, encouraged by government policies, fiscal incentives, and emissions laws to control air pollution, there has been the collateral effect of generating massive amounts of crude glycerol, a by-product from the biodiesel industry. The positive effect of minimizing CO2 emissions using biofuels is jeopardized by the fact that the waste generated by this industry represents an enormous environmental disadvantage. The strategy of viewing “waste as a resource” led the scientific community to propose numerous processes that use glycerol as raw material. Solketal, the product of the reaction of glycerol and acetone, stands out as a promising fuel additive capable of enhancing fuel octane number and oxidation stability, diminishing particle emissions and gum formation, and enhancing properties at low temperatures. The production of this chemical can rely on several of the Green Chemistry principles, besides fitting the Circular Economy Model, once it can be reinserted in the biofuel production chain. This paper reviews the recent advances in solketal production, focusing on continuous production processes and on Process Intensification strategies. The performance of different catalysts under various operational conditions is summarized and the proposed industrial solketal production processes are compared.
在政府政策、财政激励和控制空气污染的排放法律的鼓励下,全球生物柴油产量以前所未有的速度增长,产生了大量粗甘油的附带效应,这是生物柴油工业的副产品。使用生物燃料最大限度地减少二氧化碳排放的积极影响受到了这个行业产生的废物对环境的巨大不利这一事实的危害。将“废物视为资源”的策略导致科学界提出了许多以甘油为原料的工艺。Solketal是甘油和丙酮反应的产物,是一种很有前途的燃料添加剂,能够提高燃料的辛烷值和氧化稳定性,减少颗粒排放和胶质形成,并提高低温下的性能。这种化学品的生产除了符合循环经济模型外,还可以依靠绿色化学的几个原则,一旦它可以重新插入生物燃料生产链中。本文综述了溶胶生产的最新进展,重点介绍了连续生产工艺和工艺强化策略。总结了不同催化剂在不同操作条件下的性能,并对提出的工业溶剂生产工艺进行了比较。
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引用次数: 21
Lignocellulosic-Based Sorbents: A Review 木质纤维素基吸附剂:综述
Pub Date : 2021-04-10 DOI: 10.3390/SUSCHEM2020016
K. Asemave, L. Thaddeus, Philip T. Tarhemba
The combustion of fossil fuels is intensifying global warming and destructing the ecosystem with negative human health impacts as well. Even so, other anthropogenic activities have unfortunately constituted pollution also to our environment, say, in the form of waste waters. Beside these, the existing technologies for waste water treatment have problems such as high costs, sludge disposal challenges, etc. Thus, it is now important to find economically viable and safe alternatives to decontaminate waste waters. Hence, low cost, renewable, easily accessible, and readily prepared biosorbents have become favourable alternatives to traditional counterpart for the elimination of pollutants from aqueous systems. Fortunately, these biosorbents also have requisite and comparable properties necessary for adsorption of pollutants. Many studies have been reported on the application of biosorbents for pollutants removal. However, this paper provides an overview of biosorbents preparation, properties, their applications in pollutants removal and related use. Biosorbents are usually used in raw or processed forms such as activated carbon (AC), biobar (BC), and charcoal (CC) for removal of pharmaceuticals, pesticides, organics, inorganics, mycotoxins, etc. from aqueous systems. Besides classical sorption of the pollutants, biosorbents have prospect of applications as electrodes in the microbial fuel cells, green packaging materials, energy storage devices, catalysts, soil remediation agent, carbon sequestration, etc. Hence, further concerted investigations should be exercised to develop feasibly best conditions for the preparations and modifications of biosorbents. In addition, mean pore size, pore size distribution, porosity, surface functionality, and zeta potential studies are necessary to be had about biosorbents, especially novel types. There is need for development of biosorbents for specific tasks. Another essential thing is to determine desorption studies of these novel biosorbents. Focus should also be directed on more economically viable and sustainable biosorbents to enhance their use. Again, it is suggested that more suitable biomasses be identified to enable successful preparation of efficient biosorbents. More so, biosorbents can be recycled after use to avoid littering and possible pollution.
化石燃料的燃烧加剧了全球变暖,破坏了生态系统,也对人类健康产生了负面影响。尽管如此,不幸的是,其他人为活动也对我们的环境构成了污染,例如,以废水的形式。除此之外,现有的废水处理技术还存在成本高、污泥处理困难等问题。因此,现在重要的是找到经济上可行和安全的方法来净化废水。因此,低成本、可再生、易于获取和易于制备的生物吸附剂已成为消除水系统污染物的传统对应物的有利替代品。幸运的是,这些生物吸附剂也具有吸附污染物所必需的和可比的特性。生物吸附剂在污染物去除中的应用研究已经有很多报道。本文综述了生物吸附剂的制备、性能、在污染物去除中的应用及相关用途。生物吸附剂通常以原料或加工形式使用,如活性炭(AC)、生物棒(BC)和木炭(CC),用于从水系统中去除药物、农药、有机物、无机物、真菌毒素等。除传统的污染物吸附外,生物吸附剂在微生物燃料电池电极、绿色包装材料、储能装置、催化剂、土壤修复剂、固碳等方面具有广阔的应用前景。因此,应该进行进一步的协同研究,以制定可行的最佳条件来制备和改性生物吸附剂。此外,平均孔径、孔径分布、孔隙率、表面功能和zeta电位的研究是生物吸附剂,特别是新型生物吸附剂的必要研究。有必要开发用于特定任务的生物吸附剂。另一个重要的事情是确定这些新型生物吸附剂的解吸研究。还应把重点放在经济上更可行和可持续的生物吸附剂上,以加强其使用。再次,建议确定更合适的生物质,以便成功制备高效的生物吸附剂。更重要的是,生物吸附剂在使用后可以回收,以避免垃圾和可能的污染。
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引用次数: 13
Green Chemistry Approach for Fabrication of Polymer Composites 绿色化学方法制备高分子复合材料
Pub Date : 2021-04-09 DOI: 10.3390/SUSCHEM2020015
B. Joseph, Saravanan Krishnan, Sagarika Vadakke Kavil, A. R. Pai, Jemy James, N. Kalarikkal, Sabu Thomas
Solvents are an inevitable part of industries. They are widely used in manufacturing and processing industries. Despite the numerous controlling measures taken, solvents contaminate our environment to a vast extent. Green and sustainable solvents have been a matter of growing interest within the research community over the past few years due to the increasing environmental concerns. Solvents are categorized as “green” based on their nonvolatility, nonflammability, availability, biodegradability and so on. The use of ionic liquids, super critical carbon dioxide and aqueous solvents for the fabrication of polymer composites is discussed in this review. The progress of utilizing solvent-free approaches for polymer composite preparation and efforts to produce new biobased solvents are also summarized.
溶剂是工业不可避免的一部分。它们广泛应用于制造业和加工业。尽管采取了许多控制措施,溶剂还是在很大程度上污染了我们的环境。在过去的几年里,由于环境问题的日益严重,绿色和可持续溶剂已经成为研究界越来越感兴趣的问题。溶剂根据其不挥发性、不可燃性、可用性、可生物降解性等被归类为“绿色”。综述了离子液体、超临界二氧化碳和水溶剂在聚合物复合材料制备中的应用。综述了利用无溶剂方法制备聚合物复合材料的研究进展和制备新型生物基溶剂的研究进展。
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引用次数: 5
Food Waste Digestate-Based Biorefinery Approach for Rhamnolipids Production: A Techno-Economic Analysis 基于食物垃圾消化物的鼠李糖脂生物炼制方法:技术经济分析
Pub Date : 2021-04-08 DOI: 10.3390/SUSCHEM2020014
R. D. Patria, J. Wong, Davidraj Johnravindar, Kristiadi Uisan, Rajat Kumar, Guneet Kaur
The present work evaluates the techno-economic feasibility of a rhamnolipids production process that utilizes digestate from anaerobic digestion (AD) of food waste. Technical feasibility, profitability and extent of investment risks between fermenter scale and its operating strategy for rhamnolipids production was investigated in the present study. Three scenarios were generated and compared: production using a single large fermenter (Scenario I), using two small fermenters operated alternately (Scenario II) or simultaneously (Scenario III). It was found that all the scenarios were economically feasible, and Scenario III was the most profitable since it allowed the most optimum fermenter operation with utilization of multiple small-scale equipment to reduce the downtime of each equipment and increase the production capacity and overall productivity. It had the highest net present value, internal rate of return and shortest payback time at a discount rate of 7%. Finally, a sensitivity analysis was conducted to indicate how the variation in factors such as feedstock (digestate) cost, rhamnolipids selling price, extractant recyclability and process capacity influenced the process economics. The work provides important insights on techno-economic performance of a food waste digestate valorization process which would be useful to guide its sustainable scale-up.
本工作评估了利用食物垃圾厌氧消化(AD)的消化液生产鼠李糖脂的技术经济可行性。研究了鼠李糖脂生产的技术可行性、盈利能力和投资风险程度。生成并比较了三种场景:使用单个大型发酵罐(场景I),使用两个小型发酵罐交替运行(场景II)或同时运行(场景III)进行生产。发现所有场景在经济上都是可行的,并且场景III是最有利可图的,因为它允许最优的发酵罐运行,利用多个小型设备来减少每个设备的停机时间,提高生产能力和整体生产率。它的净现值最高,内部收益率最高,投资回收期最短,贴现率为7%。最后,进行了敏感性分析,以表明原料(消化液)成本、鼠李糖脂销售价格、萃取剂可回收性和工艺容量等因素的变化对工艺经济的影响。这项工作提供了对食物垃圾消化增值过程的技术经济绩效的重要见解,这将有助于指导其可持续扩大规模。
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引用次数: 6
Alkali Iodide Deep Eutectic Solvents as Alternative Electrolytes for Dye Sensitized Solar Cells 碘化碱深共晶溶剂作为染料敏化太阳能电池的替代电解质
Pub Date : 2021-04-06 DOI: 10.3390/SUSCHEM2020013
Hugo Cruz, A. L. Pinto, N. Jordão, L. Neves, L. Branco
Different alkali deep eutectic solvents (DES), such as LiI:nEG, NaI:nEG, and KI:nEG, have been tested as electrolytes for dye sensitized solar cells (DSSCs). These DSSCs were prepared using pure DES or, alternatively, DES combined with different amounts of iodine (I2). The most important parameters, such as open circuit voltage (VOC), short circuit current density (JSC), fill factor (FF), and the overall conversion efficiency (η), were evaluated. Some DES seem to be promising candidates for DSSC applications, since they present higher VOC (up to 140 mV), similar FF values but less current density values, when compared with a reference electrolyte in the same experimental conditions. Additionally, electrochemical impedance spectroscopy (EIS) has been performed to elucidate the charge transfer and transport processes that occur in DSSCs. The values of different resistance (Ω·cm2) phenomena and recombination/relaxation time (s) for each process have been calculated. The best-performance was obtained for DES-based electrolyte, KI:EG (containing 0.5 mol% I2) showing an efficiency of 2.3%. The efficiency of this DES-based electrolyte is comparable to other literature systems, but the device stability is higher (only after seven months the performance of the device drop to 60%).
不同的碱深共晶溶剂(DES),如LiI:nEG, NaI:nEG和KI:nEG,已被测试作为染料敏化太阳能电池(DSSCs)的电解质。这些DSSCs是用纯DES或DES与不同量的碘(I2)结合制备的。对开路电压(VOC)、短路电流密度(JSC)、填充系数(FF)和总转换效率(η)等重要参数进行了评价。一些DES似乎是DSSC应用的有希望的候选者,因为在相同的实验条件下,与参考电解质相比,它们具有更高的VOC(高达140 mV),相似的FF值,但电流密度值更小。此外,电化学阻抗谱(EIS)已被用于阐明发生在DSSCs中的电荷转移和输运过程。计算了每个过程的不同电阻(Ω·cm2)现象值和复合/弛豫时间(s)。以KI:EG(含0.5 mol% I2)为基料的电解液效率最高,为2.3%。这种基于des的电解质的效率与其他文献系统相当,但器件稳定性更高(仅在7个月后器件性能下降到60%)。
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引用次数: 7
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Sustainable Chemistry
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