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Optical constants manipulation of formamidinium lead iodide perovskites: ellipsometric and spectroscopic twigging. 操纵甲脒碘化铅包晶石的光学常数:椭偏和光谱分析。
IF 3.2 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-26 DOI: 10.1039/d4ya00339j
Mohd Taukeer Khan, Muhammed P U Haris, Baraa Alhouri, Samrana Kazim, Shahzada Ahmad

Unraveling the knowledge of the complex refractive index and photophysical properties of the perovskite layer is paramount to uncovering the physical process that occurs in a perovskite solar cell under illumination. Herein, we probed the optical and photophysical properties of FAPbI3 (FAPI) and Cs0.1FA0.9PbI3 (CsFAPI) thin films deposited from pre-synthesized powder, by the spectroscopic ellipsometer and time-resolved fluorescence spectra. We determined the complex refractive index of perovskite films by fitting the measured spectroscopic ellipsometer data with the three-oscillator Tauc-Lorentz (T-L) model. We deduced that the CsFAPI thin film had a slightly lower absorption coefficient than the FAPI, but a higher refractive index and dielectric constant than the FAPI. The peak photoluminescence (PL) emission of FAPI and CsFAPI thin film on glass substrates was observed around 803 nm and 799 nm, respectively, while on ITO substrates, both FAPI and CsFAPI thin film was quenched and red-shifted to 816 nm. The methylammonium free pure CsFAPI-based perovskite solar cell fabricated in p-i-n configuration, measured a competitive efficiency of 16.14%, characterized by a J SC of 23.995 mA cm-2, V OC of 912 mV, and FF of 73.74%.

了解透辉石层的复杂折射率和光物理性质对于揭示透辉石太阳能电池在光照下的物理过程至关重要。在此,我们通过光谱椭偏仪和时间分辨荧光光谱,探测了由预合成粉末沉积而成的 FAPbI3 (FAPI) 和 Cs0.1FA0.9PbI3 (CsFAPI) 薄膜的光学和光物理性质。我们用三振子陶克-洛伦兹(T-L)模型拟合光谱椭偏仪的测量数据,从而确定了包晶薄膜的复折射率。我们推断 CsFAPI 薄膜的吸收系数略低于 FAPI,但折射率和介电常数高于 FAPI。在玻璃衬底上,FAPI 和 CsFAPI 薄膜的光致发光(PL)峰值分别在 803 纳米和 799 纳米附近,而在 ITO 衬底上,FAPI 和 CsFAPI 薄膜均被淬灭并红移至 816 纳米。以 pi-n 配置制造的不含甲基铵的纯 CsFAPI 型过氧化物太阳能电池测得的竞争效率为 16.14%,J SC 为 23.995 mA cm-2,V OC 为 912 mV,FF 为 73.74%。
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引用次数: 0
Highly conductive flat grains of cesium lead bromide perovskites via additive engineering with methylammonium bromide 通过溴化甲基铵添加工程获得高导电性扁平溴化铯铅包晶石晶粒
Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-26 DOI: 10.1039/d4ya00487f
Chandra Shakher Pathak, Deepak Aloysius, Satyajit Gupta, Sabyasachi Mukhopadhyay, Eran Edri
Perovskite solar cells made of inorganic cesium lead bromide (CsPbBr3) display unusually high open-circuit potentials. Yet, their photovoltaic efficiency is still lagging behind that of iodide-based halide perovskites. In this study, a multistep solution spin coating process is used to create a CsPbBr3 film. The CsPbBr3 perovskite film consists of flat and rounded grains, and the photocurrent of each grain type is imbalanced. Interestingly, a significant current increase in flat grains is observed when conducting atomic force microscopy (c-AFM) at the nanoscale after the addition of methyl ammonium bromide (MABr) as an additive. The addition of MABr results in good optoelectronic quality of perovskite films with highly conductive grains and enables better charge transport and hence improved power conversion efficiency.
由无机溴化铯铅(CsPbBr3)制成的过氧化物太阳能电池显示出异常高的开路电位。然而,它们的光电效率仍然落后于碘化卤化物类包晶石。本研究采用多步溶液旋涂工艺制作了 CsPbBr3 薄膜。CsPbBr3 包晶薄膜由扁平和圆形晶粒组成,每种晶粒类型的光电流都不平衡。有趣的是,添加甲基溴化铵(MABr)作为添加剂后,在纳米尺度上进行原子力显微镜(c-AFM)观察时,发现扁平晶粒的电流明显增加。添加 MABr 后,具有高导电性晶粒的过氧化物薄膜具有良好的光电质量,能更好地传输电荷,从而提高功率转换效率。
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引用次数: 0
Selective kinetic control of interfacial charge transfer reactions in Si-composite anodes for Li-ion batteries† 锂离子电池硅复合材料阳极中界面电荷转移反应的选择性动力学控制†。
IF 3.2 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-23 DOI: 10.1039/D4YA00418C
Emma A. Cave, Tyson A. Carr and Cody W. Schlenker

In this report, we demonstrate a strategy to selectively suppress reactions at unpassivated active material surfaces in silicon composite electrodes, mitigating the capacity-draining effects of continual electrolyte reduction in alloying-type anodes for lithium-ion batteries. Inspired by dipolar modification of electrodes for photovoltaic applications, we introduced conformationally-labile permanent dipoles at the electrochemical electrode interface to dynamically modulate charge transfer kinetics across the interface. Polyacrylic acid (PAA) binder modified with the dipole-bearing molecule 3-cyanopropyltriethoxysilane displays a 17% increase in capacity retention versus unmodified PAA binder. Differential capacity analysis shows a marked cathodic shift of ∼150 mV in overpotential in the pre-alloying voltage range following the initial solid electrolyte interphase (SEI) formation step. At the same time, we observe negligible shift in overpotential for reversible lithium-ion storage, consistent with selective modulation of irreversible reaction kinetics. Electrochemical impedance spectroscopy indicates that this modification results in a thinner SEI layer. Despite the improved performance, the charge transfer resistance of the half-cell is higher with the modification, suggesting some opportunity for improving the strategy. Time-resolved spectroelectrochemical analysis of desolvation kinetics in modified binders indicates that the modified binder has slower and less selective ion transport. We conclude that future iterations of this strategy which avoid disrupting the beneficial ionic transport properties of the binder would result in even greater performance enhancement. We propose that this may be accomplished by incorporating oligomeric dipolar modifiers, either in the binder or at the active material itself. Either way would increase the ratio of dipoles to PAA linking sites, thus avoiding the competing deleterious impacts on device performance.

在本报告中,我们展示了一种选择性抑制硅复合电极中未钝化活性材料表面反应的策略,从而减轻了合金型锂离子电池阳极中电解液持续还原对容量的影响。受用于光伏应用的电极偶极改性的启发,我们在电化学电极界面上引入了构象稳定的永久偶极,以动态调节跨界面的电荷转移动力学。用偶极分子 3-氰丙基三乙氧基硅烷修饰的聚丙烯酸(PAA)粘合剂与未修饰的聚丙烯酸粘合剂相比,容量保持率提高了 17%。差分容量分析表明,在最初的固体电解质相(SEI)形成步骤之后,合金化前电压范围内的过电位发生了明显的阴极转变,转变幅度为 150 mV。与此同时,我们观察到在可逆锂离子存储过程中过电位的移动微乎其微,这与不可逆反应动力学的选择性调节是一致的。电化学阻抗光谱表明,这种改性导致 SEI 层变薄。尽管性能有所改善,但改性后半电池的电荷转移电阻较高,这表明该策略还有改进的余地。对改性粘合剂中脱溶动力学的时间分辨光谱电化学分析表明,改性粘合剂的离子传输速度较慢,选择性较差。我们得出的结论是,这种策略的未来迭代如果能避免破坏粘合剂有益的离子传输特性,将会带来更大的性能提升。我们建议,可以通过在粘合剂中或活性材料本身加入低聚双极性改性剂来实现这一目标。无论采用哪种方法,都能提高偶极与 PAA 连接位点的比例,从而避免对器件性能产生有害的竞争性影响。
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引用次数: 0
A cradle-to-gate life cycle assessment of green methanol production using direct air capture† 利用直接空气捕集技术进行绿色甲醇生产的 "从摇篮到终点 "生命周期评估†。
IF 3.2 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-20 DOI: 10.1039/D4YA00316K
Nicholas Badger, Rahim Boylu, Valentine Ilojianya, Mustafa Erguvan and Shahriar Amini

This study presents a comprehensive cradle-to-gate life cycle assessment (LCA) of synthetic methanol production, integrating low-temperature solid sorbent direct air capture (DAC) systems with renewable energy sources and green hydrogen to evaluate the environmental impacts of various renewable energy configurations for powering the DAC-to-methanol synthesis processes. Renewable energy-powered configurations result in significantly lower greenhouse gas (GHG) emissions than traditional methanol production methods and DAC systems powered by conventional grid energy. Energy configurations analyzed are current US grid mix, solar photovoltaic (PV) in Alabama and Arizona, USA, onshore wind, run-of-river hydroelectric, and geothermal. Notably, hydroelectric and wind power in the western United States emerge as the most sustainable options, showing the lowest global warming potential (GWP) impacts at −2.53 and −2.39 kg CO2 eq. per kg methanol produced, respectively, in contrast to the +0.944 kg CO2 eq. from traditional steam methane reforming. Furthermore, this research investigates the use of various heat sources for regenerating low-temperature solid sorbent DAC, emphasizing the potential integration of new experimental results of novel microwave-based regeneration compared to industrial waste heat. Through the analysis of renewable energy scenarios and DAC regeneration heat sources, the research emphasizes the pivotal role of sustainable energy sources in climate change mitigation. This study introduces a new approach by comparing both various renewable energy sources and DAC heat sources to identify the most optimal configurations. This work is also distinguished by its integration of new experimental data on microwave DAC regeneration, offering a unique contribution to the existing body of knowledge. This LCA scrutinizes the environmental impacts of renewably powered DAC-to-methanol systems and compares them with traditional methanol production methods, revealing the significant potential for carbon neutrality. The findings highlight the importance of strategic technology and energy source optimization to minimize environmental impacts, thus guiding the scaling up of DAC and renewable energy technologies for effective climate mitigation. By recognizing the environmental advantages of integrating renewable energy sources with DAC-to-methanol technologies, this research marks a significant step forward in advancing DAC technology and pushes the boundaries of green methanol production toward true sustainability.

本研究对合成甲醇生产进行了全面的 "从摇篮到终点 "生命周期评估(LCA),将低温固体吸附剂直接空气捕集(DAC)系统与可再生能源和绿色氢气相结合,以评估各种可再生能源配置对 DAC 到甲醇合成过程的环境影响。与传统甲醇生产方法和以传统电网能源为动力的 DAC 系统相比,以可再生能源为动力的配置大大降低了温室气体(GHG)排放量。所分析的能源配置包括当前的美国电网组合、美国阿拉巴马州和亚利桑那州的太阳能光伏 (PV)、陆上风能、径流式水电和地热。值得注意的是,美国西部的水力发电和风力发电是最具可持续性的选择,其全球升温潜能值(GWP)影响最低,分别为每千克甲醇生产-2.53 千克二氧化碳当量和-2.39 千克二氧化碳当量,而传统的蒸汽甲烷转化则为+0.944 千克二氧化碳当量。此外,本研究还调查了使用各种热源再生低温固体吸附剂 DAC 的情况,强调了与工业废热相比,基于微波的新型再生实验结果的整合潜力。通过分析可再生能源方案和 DAC 再生热源,该研究强调了可持续能源在减缓气候变化中的关键作用。这项研究引入了一种新方法,通过比较各种可再生能源和 DAC 热源,找出最佳配置。这项工作的另一个特点是整合了微波 DAC 再生的新实验数据,为现有知识体系做出了独特的贡献。该生命周期评估仔细研究了可再生动力 DAC 转甲醇系统对环境的影响,并将其与传统甲醇生产方法进行了比较,揭示了实现碳中和的巨大潜力。研究结果强调了对技术和能源进行战略性优化的重要性,以最大限度地减少对环境的影响,从而指导扩大 DAC 和可再生能源技术的规模,有效减缓气候变化。通过认识到将可再生能源与 DAC 转化甲醇技术相结合的环境优势,这项研究标志着在推进 DAC 技术方面迈出了重要一步,并将绿色甲醇生产推向了真正的可持续发展。
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引用次数: 0
Analysis of the impact of remote oxygen plasma treatment on the surface chemistry and electrochemical properties of graphite felt electrodes for redox flow batteries 分析远程氧等离子处理对氧化还原液流电池石墨毡电极表面化学和电化学特性的影响
Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-19 DOI: 10.1039/d4ya00383g
L. Mauricio Murillo-Herrera, Carlos J. Mingoes, J. Obrero-Pérez, Juan R. Sánchez-Valencia, Michael W. Thielke, Ángel Barranco, Ana B. Jorge Sobrido
The effects of a remote oxygen plasma (ROP) treatment on the surface of commercial graphite felts were investigated and compared against a conventional thermal treatment. In contrast to methodologies where the sample is directly exposed to the plasma, ROP allows for a high control of sample–plasma interaction, thereby avoiding extensive etching processes on the fibre surface. To assess the impact of ROP treatment time, the electrodes were subjected to three different periods (10, 60, and 600 seconds). X-ray photoelectron spectroscopy showed that the ROP treatment introduced nearly three times more surface oxygen functionalities than the thermal treatment. Raman spectroscopy measurements revealed a significant increase in amorphous carbon domains for the ROP samples. The thermal treatment favoured increases in graphitic defects and resulted in an order of magnitude larger ECSA compared to the ROP treated materials despite having lower content in oxygen functionalities. The electrochemical analysis showed enhanced charge-transfer overpotentials for GF400. The ROP samples exhibited a lower mass-transport overpotential than the thermally treated material and had similar permeabilities, which overall translated to the thermal treatment offering better performance at fast flow rates. However, at slow flow rates (∼10 mL min−1), the ROP treatment for the shortest period offered comparable performance to conventional thermal treatment.
研究了远程氧等离子体(ROP)处理对商用石墨毡表面的影响,并与传统热处理进行了比较。与将样品直接暴露在等离子体中的方法不同,远程氧等离子体可对样品与等离子体之间的相互作用进行高度控制,从而避免纤维表面的大量蚀刻过程。为了评估 ROP 处理时间的影响,对电极进行了三个不同时间段的处理(10 秒、60 秒和 600 秒)。X 射线光电子能谱显示,ROP 处理所引入的表面氧官能度几乎是热处理的三倍。拉曼光谱测量显示,ROP 样品的无定形碳域显著增加。热处理有利于石墨缺陷的增加,与 ROP 处理的材料相比,尽管氧官能团含量较低,但 ECSA 却大了一个数量级。电化学分析表明,GF400 的电荷转移过电位有所提高。与热处理材料相比,ROP 样品的质量传输过电位更低,而渗透率却相差无几。然而,在低流速下(10 mL min-1),ROP 处理的最短时间与传统热处理的性能相当。
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引用次数: 0
Feasibility study of UV intensity monitoring in water disinfection systems using reverse-biased LED photometers† 使用反向偏置 LED 光度计监测水消毒系统中紫外线强度的可行性研究†。
IF 3.2 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-19 DOI: 10.1039/D3YA00554B
D. Pousty, Y. Gerchman and H. Mamane

Common ultraviolet (UV) photodiodes or detectors for measuring the intensity of UV-light-emitting diodes (LEDs) in UV disinfection systems are costly. This study explores the potential of using low-cost UV-LEDs as photometers for monitoring UV intensity in water systems. Reverse LEDs (rLEDs) generate a small current proportional to the incident light intensity on the p–n junction when operated in unbiased mode. rLEDs with different wavelengths and power levels were examined to find the optimal rLED for monitoring the intensity of a 275 nm LED strip, achieving less than 1% deviation from a calibrated spectroradiometer. The influence of temperature was also examined on rLED measurements and found non-negligible. This work demonstrates the feasibility of using rLEDs as intensity monitoring sensors for UV-C LED sources, offering a low-cost and reliable alternative for UV intensity monitoring in UV-LED water disinfection systems.

用于测量紫外线消毒系统中紫外线发光二极管(LED)强度的普通紫外线(UV)光电二极管或探测器价格昂贵。本研究探讨了使用低成本紫外线发光二极管作为光度计来监测水系统中紫外线强度的潜力。反向 LED(rLED)在非偏置模式下工作时,会在 p-n 结上产生与入射光强度成比例的小电流。研究人员对不同波长和功率水平的 rLED 进行了检验,以找到监测 275 纳米 LED 灯带强度的最佳 rLED,使其与校准分光辐射计的偏差小于 1%。此外,还研究了温度对 rLED 测量的影响,结果发现这种影响不可忽略。这项工作证明了将 rLED 用作紫外线-C LED 光源强度监测传感器的可行性,为紫外线-LED 水消毒系统中的紫外线强度监测提供了一种低成本、可靠的替代方法。
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引用次数: 0
Sustainable fermentable sugar production using a glass fiber supported gallium–molybdenum photocatalyst towards bioethanol production: LCA analysis 利用玻璃纤维支撑的镓钼光催化剂生产生物乙醇,实现可持续发酵糖生产:生命周期评估分析
Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-16 DOI: 10.1039/d4ya00226a
Rajat Chakraborty, Sourav Barman, Aritro Sarkar
For the first time, a cost-effective glass fiber (GF) support derived from waste printed circuit boards (W-PCBs) was utilized to synthesize a reusable GF-supported gallium–molybdenum photocatalyst (GaMo–GF) for generating fermentable sugar (FS) from delignified corncob (DCC) in a quartz halogen solar batch reactor (QHSR). Additionally, this paper presents a comparative detoxification investigation and subsequent fermentation of the resulting FS using Pichia stipitis. The optimum Ga4Mo-GF (with a gallium precursor loading of 4 wt%) photocatalyst exhibited impressive characteristics, including a high specific surface area (28.01 m2 g−1), high pore volume (0.04198 cc g−1) and lower band gap energy (2.3 eV), providing a maximum 78.35 mol% FS yield under mild reaction conditions (100 °C and 20 min) with mild energy consumption (12 kJ mL−1). The comparative hydrolysate detoxification study highlighted the superior efficacy of the Amberlite IRP69 cation resin, achieving maximum removal rates of 86% for furfural, 92% for formic acid, and 95% for levulinic acid compared to other methods. Furthermore, the hydrolysate detoxified using Amberlite IRP69 resulted in a higher bioethanol concentration (4.32 mmol mL−1) compared to NaOH neutralization (3.06 mmol mL−1), Ca(OH)2 over-liming (2.88 mmol mL−1), and ethyl acetate solvent extraction (3.73 mmol mL−1) when fermented with Pichia stipitis. Additionally, the overall environmental impact assessment indicated that utilizing the Amberlite IRP69 cation resin not only enhanced bioethanol yield but also reduced environmental impacts. Remarkably, the optimized Ga4Mo-GF catalyst demonstrated reusability for up to 7 cycles in the DCC hydrolysis process, showcasing its stability and the consequential reduction in environmental impacts throughout the corncob to bioethanol conversion process.
本文首次利用从废弃印刷电路板(W-PCBs)中提取的具有成本效益的玻璃纤维(GF)载体,合成了一种可重复使用的玻璃纤维载体镓钼光催化剂(GaMo-GF),用于在石英卤素太阳能批式反应器(QHSR)中从脱木质素玉米芯(DCC)中生成可发酵糖(FS)。此外,本文还介绍了一项比较解毒研究,以及随后使用 Pichia stipitis 对所产生的可发酵糖进行发酵。最佳 Ga4Mo-GF(镓前体负载量为 4 wt%)光催化剂表现出令人印象深刻的特性,包括高比表面积(28.01 m2 g-1)、高孔隙率(0.04198 cc g-1)和较低的带隙能(2.3 eV),在温和的反应条件下(100 °C、20 分钟),能耗较低(12 kJ mL-1),可提供最高 78.35 mol% 的 FS 产量。水解物解毒对比研究凸显了 Amberlite IRP69 阳离子树脂的卓越功效,与其他方法相比,糠醛的最大去除率为 86%,甲酸的最大去除率为 92%,乙酰丙酸的最大去除率为 95%。此外,在使用 Pichia stipitis 发酵时,与 NaOH 中和法(3.06 mmol mL-1)、Ca(OH)2 超限法(2.88 mmol mL-1)和乙酸乙酯溶剂萃取法(3.73 mmol mL-1)相比,使用 Amberlite IRP69 进行解毒的水解物产生了更高的生物乙醇浓度(4.32 mmol mL-1)。此外,整体环境影响评估表明,使用 Amberlite IRP69 阳离子树脂不仅能提高生物乙醇产量,还能减少对环境的影响。值得注意的是,经过优化的 Ga4Mo-GF 催化剂在 DCC 水解过程中可重复使用长达 7 个周期,这证明了其稳定性以及在玉米芯到生物乙醇的整个转化过程中对环境影响的相应减少。
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引用次数: 0
Effect of process parameters on woody biomass fractionation in a methanol/water mixture in a semi-flow reactor 半流式反应器中甲醇/水混合物的工艺参数对木质生物质分馏的影响
Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-14 DOI: 10.1039/d4ya00261j
Yilin Yao, Eiji Minami, Haruo Kawamoto
The degradation of woody biomass in methanol/water mixtures at elevated temperatures and pressures is a promising candidate for chemical production from renewable resources, combining the wood-degrading ability of water with the product-dissolving capacity of methanol. However, the effects of water and methanol on wood degradation remain unclear. In the present study, the effect of process parameters on the degradation of Japanese cedar in methanol/water at 270 °C and 10–30 MPa was investigated using a semi-flow reactor in which pressure and temperature can be controlled independently. At 270 °C, hemicelluloses were degraded and solubilized more preferentially at 10 MPa, but delignification was more preferred at 20 and 30 MPa. In the resulting products, methylation of coniferyl alcohol from lignin and methyl esterification of methyl glucuronopentosan from hemicellulose were more advanced at 20 and 30 MPa than at 10 MPa. These results suggest that at 10 MPa the influence of water is dominant and promotes polysaccharide degradation, whereas at 20 and 30 MPa the influence of methanol is dominant and promotes delignification. Our findings will provide insight into the establishment of efficient chemical production from woody biomass with solvolysis technology.
木质生物质在高温高压的甲醇/水混合物中降解,是利用可再生资源生产化学品的一个很有前景的候选方案,它结合了水的木材降解能力和甲醇的产品溶解能力。然而,水和甲醇对木材降解的影响仍不清楚。本研究使用压力和温度可独立控制的半流反应器,在 270 °C 和 10-30 兆帕的条件下,研究了工艺参数对日本杉在甲醇/水中降解的影响。在 270 °C 的条件下,10 兆帕时半纤维素更容易降解和溶解,而 20 和 30 兆帕时则更容易木质素化。在生成物中,木质素的针叶醇甲基化和半纤维素的甲基葡糖酸戊聚糖甲基酯化在 20 和 30 兆帕时比在 10 兆帕时更快。这些结果表明,在 10 兆帕时,水的影响占主导地位并促进多糖降解,而在 20 和 30 兆帕时,甲醇的影响占主导地位并促进脱木素。我们的研究结果将为利用溶解技术从木质生物质中高效生产化学品提供启示。
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引用次数: 0
Acid–base concentration swing for direct air capture of carbon dioxide† 直接空气捕集二氧化碳的酸碱浓度摆动†
IF 3.2 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-13 DOI: 10.1039/D4YA00251B
Anatoly Rinberg and Michael J. Aziz

This work demonstrates the first experimental evidence of the acid–base concentration swing (ABCS) for direct air capture of CO2. This process is based on the effect that concentrating particular acid–base chemical reactants will strongly acidify solution, through Le Chatelier's principle, and result in outgassing absorbed CO2. After collecting the outgassed CO2, diluting the solution will result in a reversal of the acid–base reaction, basifying the solution and allowing for atmospheric CO2 absorption. The experimental study examines a system that includes sodium cation as the alkalinity carrier, boric acid, and a polyol complexing agent that reversibly reacts with boric acid to strongly acidify solution upon concentration. Though the tested experimental system faces absorption rate and water capacity limitations, the ABCS process described here provides a basis for further process optimization. A generalized theoretical ABCS reaction framework is developed and different reaction orders and conditions are studied mathematically. Higher order reactions yield favorable cycle output results, reaching volumetric cycle capacity above 50 mM for third-order and 80 mM for fourth-order reactions. Optimal equilibrium constants are determined in order to guide alternative chemical searches and synthetic chemistry design targets. There is a substantial energetic benefit for reaction orders above the first, with second- and third-order ABCS cycles exhibiting a thermodynamic minimum work for the concentrating and outgassing steps around 150 kJ per mole of CO2. A significant advantage of the ABCS is that it can be driven through well-developed and widely-deployed desalination technologies, such as reverse osmosis, with opportunities for energy recovery when recombining the concentrated and diluted streams, and extraction can occur directly from the liquid phase upon vacuum application.

这项工作首次证明了酸碱浓度摆动(ABCS)在直接空气捕获二氧化碳方面的实验证据。这一过程基于以下效应:通过勒夏特列原理,浓缩特定的酸碱化学反应物会使溶液强烈酸化,并导致吸收的二氧化碳排气。收集排出的二氧化碳后,稀释溶液将导致酸碱反应逆转,使溶液碱化,并允许吸收大气中的二氧化碳。实验研究考察的系统包括作为碱度载体的阳离子钠、硼酸和多元醇络合剂,后者与硼酸发生可逆反应,在浓缩后使溶液强酸化。虽然测试的实验系统面临着吸收率和水容量的限制,但这里描述的 ABCS 工艺为进一步优化工艺提供了基础。我们建立了一个广义的 ABCS 反应理论框架,并对不同的反应阶次和条件进行了数学研究。高阶反应产生了良好的循环输出结果,三阶反应的体积循环容量超过 50 毫摩尔,四阶反应的体积循环容量超过 80 毫摩尔。确定了最佳平衡常数,以指导替代化学搜索和合成化学设计目标。一阶以上的反应具有很大的能量优势,二阶和三阶 ABCS 循环在浓缩和排气步骤中的热力学最小功约为每摩尔二氧化碳 150 千焦。ABCS 的一个显著优势是,它可以通过成熟且广泛应用的海水淡化技术(如反渗透)来驱动,在重新混合浓缩流和稀释流时有机会回收能量,并且在真空应用时可以直接从液相中提取。
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引用次数: 0
Microreactor assisted soft lithography of nanostructured antimony sulfide thin film patterns: nucleation, growth and application in solid state batteries† 纳米结构硫化锑薄膜图案的微反应器辅助软光刻:固态电池中的成核、生长和应用
IF 3.2 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-12 DOI: 10.1039/D4YA00436A
Bryan Chun, V. Vinay K. Doddapaneni, Marcos Lucero, Changqing Pan, Zhongwei Gao, Zhenxing Feng, Rajiv Malhotra and Chih-hung Chang

This study explores the microreactor-assisted soft lithography (MASL) method for direct, one-step synthesis and patterning of additive-free antimony sulfide (Sb2S3) nanostructured thin films. The results reveal the steady state process and its ability to overcome the challenges and limitations of conventional solution deposition processes. This new approach, exploiting continuous flow, prevents the dissolution of the growing film, a common issue in batch solution deposition methods. Furthermore, this study successfully fabricates functional Sb2S3–Li coin cell prototypes, demonstrating stable specific capacities of 600 mA h g−1 for over 260 cycles at a C/2 charge rate and coulombic efficiencies of 96–98%.

本研究探索了微反应器辅助软光刻(MASL)方法,用于一步法直接合成无添加剂硫化锑(Sb2S3)纳米结构薄膜并将其图案化。研究结果揭示了稳态工艺及其克服传统溶液沉积工艺的挑战和局限性的能力。这种利用连续流的新方法可以防止生长薄膜的溶解,而这是批量溶液沉积方法中常见的问题。此外,这项研究还成功制造出了功能性 Sb2S3-Li 纽扣电池原型,在 C/2 充电速率下超过 260 个循环中显示出 600 mAh g-1 的稳定比容量和 96-98% 的库仑效率。
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Energy advances
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