Pub Date : 2024-08-16DOI: 10.1016/j.gee.2024.08.004
Li Sun, Lujia Chai, Liangqi Jing, Yujuan Chen, Kelei Zhuo, Jianji Wang
Due to insufficient energy density, supercapacitors (SCs) with preeminent-power and long cycle stability cannot be implemented in some practical applications. Exploring hybrid materials with redox activity to emerge high specific capacitance in ionic liquid (IL) electrolytes can solve this problem. Herein, we report a redox-organic molecule 2,6-diaminoanthraquinone (DAAQ) modified MXene (TiCT)/Graphene (DAAQ-M/G) composite material. With the assist of graphene oxide (GO), MXene and graphene fabricate a three-dimensional (3D) interconnected structure as a conductive framework, which inhibits self-stacking of MXene monolayers and ensures high electronic conductivity. Meanwhile, DAAQ is loaded onto the M/G framework through covalent/non-covalent functionalization. The DAAQ as a spacer effectively enlarges the interlayer spacing of MXene nanosheets, and meanwhile produces reversible redox reactions during charge/discharge processes to provide additional Faradaic contribution to capacity. Therefore, the specific capacitance (capacity) of the DAAQ-M/G as the negative electrode material reaches to 226 F g (306 C g) at 1 A g in 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF) electrolyte. Furthermore, an asymmetric supercapacitor (ASC) is assembled using DAAQ-M/G as the negative electrode and self-prepared organic molecule hydroquinone modified reduced graphene oxide (HQ-RGO) material as the positive electrode, with a high energy density of 43 Wh kg at high power density of 1669 W kg. The ASC can maintain 80% of initial specific capacitance after 9000 cycles. This research can provide better support to develop advanced organic molecules-modified MXene composite materials for ionic liquid-based SCs.
由于能量密度不足，具有卓越功率和长周期稳定性的超级电容器（SC）在某些实际应用中无法实现。探索具有氧化还原活性的混合材料，在离子液体（IL）电解质中产生高比电容，可以解决这一问题。在此，我们报告了一种氧化还原有机分子 2,6-二氨基蒽醌（DAAQ）修饰的 MXene（TiCT）/石墨烯（DAAQ-M/G）复合材料。在氧化石墨烯（GO）的辅助下，MXene 和石墨烯形成了三维（3D）互连结构作为导电框架，从而抑制了 MXene 单层的自堆积，确保了高电子导电性。同时，通过共价/非共价官能化将 DAAQ 加载到 M/G 框架上。作为间隔物的 DAAQ 有效地扩大了 MXene 纳米片的层间间距，同时在充放电过程中产生可逆的氧化还原反应，为电容提供额外的法拉第贡献。因此，在 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF) 电解液中，DAAQ-M/G 作为负极材料的比电容（容量）在 1 A g 时达到 226 F g (306 C g)。此外，以 DAAQ-M/G 为负极，以自制备的有机分子对苯二酚修饰的还原型氧化石墨烯（HQ-RGO）材料为正极，组装了不对称超级电容器（ASC），在 1669 W kg 的高功率密度下，能量密度高达 43 Wh kg。ASC 可在 9000 次循环后保持初始比电容的 80%。这项研究可为开发先进的有机分子改性 MXene 复合材料提供更好的支持，用于离子液体型 SC。
{"title":"2,6-Diaminoanthraquinone modified MXene (Ti3C2Tx)/graphene as the negative electrode materials for ionic liquid-based asymmetric supercapacitors","authors":"Li Sun, Lujia Chai, Liangqi Jing, Yujuan Chen, Kelei Zhuo, Jianji Wang","doi":"10.1016/j.gee.2024.08.004","DOIUrl":"https://doi.org/10.1016/j.gee.2024.08.004","url":null,"abstract":"Due to insufficient energy density, supercapacitors (SCs) with preeminent-power and long cycle stability cannot be implemented in some practical applications. Exploring hybrid materials with redox activity to emerge high specific capacitance in ionic liquid (IL) electrolytes can solve this problem. Herein, we report a redox-organic molecule 2,6-diaminoanthraquinone (DAAQ) modified MXene (TiCT)/Graphene (DAAQ-M/G) composite material. With the assist of graphene oxide (GO), MXene and graphene fabricate a three-dimensional (3D) interconnected structure as a conductive framework, which inhibits self-stacking of MXene monolayers and ensures high electronic conductivity. Meanwhile, DAAQ is loaded onto the M/G framework through covalent/non-covalent functionalization. The DAAQ as a spacer effectively enlarges the interlayer spacing of MXene nanosheets, and meanwhile produces reversible redox reactions during charge/discharge processes to provide additional Faradaic contribution to capacity. Therefore, the specific capacitance (capacity) of the DAAQ-M/G as the negative electrode material reaches to 226 F g (306 C g) at 1 A g in 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF) electrolyte. Furthermore, an asymmetric supercapacitor (ASC) is assembled using DAAQ-M/G as the negative electrode and self-prepared organic molecule hydroquinone modified reduced graphene oxide (HQ-RGO) material as the positive electrode, with a high energy density of 43 Wh kg at high power density of 1669 W kg. The ASC can maintain 80% of initial specific capacitance after 9000 cycles. This research can provide better support to develop advanced organic molecules-modified MXene composite materials for ionic liquid-based SCs.","PeriodicalId":12744,"journal":{"name":"Green Energy & Environment","volume":"42 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142200003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mineral carbonation is a promising CO sequestration strategy that can utilize industrial wastes to convert CO into high-value CaCO. This review summarizes the advancements in CO mineralization using typical industrial wastes to prepare ultrafine CaCO. This work surveys the mechanisms of CO mineralization using these wastes and its capacities to synthesize CaCO, evaluates the effects of carbonation pathways and operating parameters on the preparation of CaCO, analyzes the current industrial application status and economics of this technology. Due to the large amount of impurities in solid wastes, the purity of CaCO prepared by indirect methods is greater than that prepared by direct methods. Crystalline CaCO includes three polymorphs. The polymorph of CaCO synthesized by carbonation process is determined the combined effects of various factors. These parameters essentially impact the nucleation and growth of CaCO by altering the CO supersaturation in the reaction system and the surface energy of CaCO grains. Increasing the initial pH of the solution and the CO flow rate favors the formation of vaterite, but calcite is formed under excessively high pH. Vaterite formation is favored at lower temperatures and residence time. With increased temperature and prolonged residence time, it passes through aragonite metastable phase and eventually transforms into calcite. Moreover, polymorph modifiers can decrease the surface energy of CaCO grains, facilitating the synthesis of vaterite. However, the large-scale application of this technology still faces many problems, including high costs, high energy consumption, low calcium leaching rate, low carbonation efficiency, and low product yield. Therefore, it is necessary to investigate ways to accelerate carbonation, optimize operating parameters, develop cost-effective agents, and understand the kinetics of CaCO nucleation and crystallization to obtain products with specific crystal forms. Furthermore, more studies on life cycle assessment (LCA) should be conducted to fully confirm the feasibility of the developed technologies.
{"title":"CO2 mineralization by typical industrial solid wastes for preparing ultrafine CaCO3: A review","authors":"Run Xu, Fuxia Zhu, Liang Zou, Shuqing Wang, Yanfang Liu, Jili Hou, Chenghao Li, Kuntong Song, Lingzhao Kong, Longpeng Cui, Zhiqiang Wang","doi":"10.1016/j.gee.2024.08.002","DOIUrl":"https://doi.org/10.1016/j.gee.2024.08.002","url":null,"abstract":"Mineral carbonation is a promising CO sequestration strategy that can utilize industrial wastes to convert CO into high-value CaCO. This review summarizes the advancements in CO mineralization using typical industrial wastes to prepare ultrafine CaCO. This work surveys the mechanisms of CO mineralization using these wastes and its capacities to synthesize CaCO, evaluates the effects of carbonation pathways and operating parameters on the preparation of CaCO, analyzes the current industrial application status and economics of this technology. Due to the large amount of impurities in solid wastes, the purity of CaCO prepared by indirect methods is greater than that prepared by direct methods. Crystalline CaCO includes three polymorphs. The polymorph of CaCO synthesized by carbonation process is determined the combined effects of various factors. These parameters essentially impact the nucleation and growth of CaCO by altering the CO supersaturation in the reaction system and the surface energy of CaCO grains. Increasing the initial pH of the solution and the CO flow rate favors the formation of vaterite, but calcite is formed under excessively high pH. Vaterite formation is favored at lower temperatures and residence time. With increased temperature and prolonged residence time, it passes through aragonite metastable phase and eventually transforms into calcite. Moreover, polymorph modifiers can decrease the surface energy of CaCO grains, facilitating the synthesis of vaterite. However, the large-scale application of this technology still faces many problems, including high costs, high energy consumption, low calcium leaching rate, low carbonation efficiency, and low product yield. Therefore, it is necessary to investigate ways to accelerate carbonation, optimize operating parameters, develop cost-effective agents, and understand the kinetics of CaCO nucleation and crystallization to obtain products with specific crystal forms. Furthermore, more studies on life cycle assessment (LCA) should be conducted to fully confirm the feasibility of the developed technologies.","PeriodicalId":12744,"journal":{"name":"Green Energy & Environment","volume":"25 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142200006","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-08DOI: 10.1016/j.gee.2024.08.001
Shaoxin Li, Jiajin Liu, Zhong Lin Wang, Di Wei
Traditional chemical processes often generate substantial waste, leading to significant pollution of water, air, and soil. Developing eco-friendly chemical methods is crucial for economic and environmental sustainability. Mechano-driven chemistry, with its potential for material recyclability and minimal byproducts, is well-aligned with green chemistry principles. Despite its origins over 2000 years ago and nearly 200 years of scientific investigation, mechano-driven chemistry has not been widely implemented in practice. This is likely due to a lack of comprehensive understanding and the complex physical effects of mechanical forces, which challenge reaction efficiency and scalability. This review summarizes the historical development of mechano-driven chemistry and discusses its progress across various physical mechanisms, including mechanochemistry, tribochemistry, piezochemistry, and contact electrification (CE) chemistry. CE-induced chemical reactions, involving ion transfer, electron transfer, and radical generation, are detailed, emphasizing the dominant role of radicals initiated by electron transfer and the influence of ion transfer through electrical double layer (EDL) formation. Advancing efficient, eco-friendly, and controllable green chemical technologies can reduce reliance on traditional energy sources (such as electricity and heat) and toxic chemical reagents, fostering innovation in material synthesis, catalytic technologies, and establishing a new paradigm for broader chemical applications.
{"title":"Mechano-driven chemical reactions","authors":"Shaoxin Li, Jiajin Liu, Zhong Lin Wang, Di Wei","doi":"10.1016/j.gee.2024.08.001","DOIUrl":"https://doi.org/10.1016/j.gee.2024.08.001","url":null,"abstract":"Traditional chemical processes often generate substantial waste, leading to significant pollution of water, air, and soil. Developing eco-friendly chemical methods is crucial for economic and environmental sustainability. Mechano-driven chemistry, with its potential for material recyclability and minimal byproducts, is well-aligned with green chemistry principles. Despite its origins over 2000 years ago and nearly 200 years of scientific investigation, mechano-driven chemistry has not been widely implemented in practice. This is likely due to a lack of comprehensive understanding and the complex physical effects of mechanical forces, which challenge reaction efficiency and scalability. This review summarizes the historical development of mechano-driven chemistry and discusses its progress across various physical mechanisms, including mechanochemistry, tribochemistry, piezochemistry, and contact electrification (CE) chemistry. CE-induced chemical reactions, involving ion transfer, electron transfer, and radical generation, are detailed, emphasizing the dominant role of radicals initiated by electron transfer and the influence of ion transfer through electrical double layer (EDL) formation. Advancing efficient, eco-friendly, and controllable green chemical technologies can reduce reliance on traditional energy sources (such as electricity and heat) and toxic chemical reagents, fostering innovation in material synthesis, catalytic technologies, and establishing a new paradigm for broader chemical applications.","PeriodicalId":12744,"journal":{"name":"Green Energy & Environment","volume":"31 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142225711","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An innovative strategy was proposed by integration of membrane contactor (MC) with biphasic solvent for efficient CO capture from flue gas. The accessible fly ash-based ceramic membrane (CM) underwent hydrophobic modification through silane grafting, followed by fluoroalkylsilane decoration, to prepare the superhydrophobic membrane (CSCM). The CSCM significantly improved resistance to wetting by the biphasic solvent, consisting of amine (DETA) and sulfolane (TMS). Morphological characterizations and chemical analysis revealed the notable enhancements in pore structure and hydrophobic chemical groups for the modified membrane. Predictions of wetting/bubbling behavior based on static wetting theory referred the liquid entry pressure (LEP) of CSCM increased by 20 kPa compared to pristine CM. Compared with traditional amine solvents, the biphasic solvent presented the expected phase separation. Performance experiments demonstrated that the CO capture efficiency of the biphasic solvent increased by 7%, and the electrical energy required for desorption decreased by 32%. The 60-h continuous testing and supplemental characterization of used membrane confirmed the excellent adaptability and durability of the CSCMs. This study provides a potential approach for accessing hydrophobic ceramic membranes and biphasic solvents for industrial CO capture.
通过将膜接触器（MC）与双相溶剂相结合，提出了一种从烟道气中高效捕集一氧化碳的创新策略。通过硅烷接枝对可获得的粉煤灰基陶瓷膜（CM）进行疏水改性，然后进行氟烷基硅烷装饰，制备出超疏水膜（CSCM）。CSCM 大大提高了抗双相溶剂（由胺（DETA）和砜（TMS）组成）润湿的能力。形态特征和化学分析显示，改性膜的孔隙结构和疏水化学基团明显改善。基于静态润湿理论的润湿/气泡行为预测表明，与原始 CM 相比，CSCM 的液体进入压力 (LEP) 增加了 20 kPa。与传统胺溶剂相比，双相溶剂呈现出预期的相分离现象。性能实验表明，双相溶剂的一氧化碳捕获效率提高了 7%，解吸所需的电能降低了 32%。对使用过的膜进行的 60 小时连续测试和补充表征证实了 CSCM 的出色适应性和耐用性。这项研究为利用疏水陶瓷膜和双相溶剂捕获工业 CO 提供了一种潜在的方法。
{"title":"Superhydrophobic ceramic membrane coupled with a biphasic solvent for efficient CO2 capture","authors":"Kaili Xue, Zhen Chen, Xiaona Wu, Heng Zhang, Haiping Chen, Junhua Li","doi":"10.1016/j.gee.2024.07.010","DOIUrl":"https://doi.org/10.1016/j.gee.2024.07.010","url":null,"abstract":"An innovative strategy was proposed by integration of membrane contactor (MC) with biphasic solvent for efficient CO capture from flue gas. The accessible fly ash-based ceramic membrane (CM) underwent hydrophobic modification through silane grafting, followed by fluoroalkylsilane decoration, to prepare the superhydrophobic membrane (CSCM). The CSCM significantly improved resistance to wetting by the biphasic solvent, consisting of amine (DETA) and sulfolane (TMS). Morphological characterizations and chemical analysis revealed the notable enhancements in pore structure and hydrophobic chemical groups for the modified membrane. Predictions of wetting/bubbling behavior based on static wetting theory referred the liquid entry pressure (LEP) of CSCM increased by 20 kPa compared to pristine CM. Compared with traditional amine solvents, the biphasic solvent presented the expected phase separation. Performance experiments demonstrated that the CO capture efficiency of the biphasic solvent increased by 7%, and the electrical energy required for desorption decreased by 32%. The 60-h continuous testing and supplemental characterization of used membrane confirmed the excellent adaptability and durability of the CSCMs. This study provides a potential approach for accessing hydrophobic ceramic membranes and biphasic solvents for industrial CO capture.","PeriodicalId":12744,"journal":{"name":"Green Energy & Environment","volume":"23 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A two-stage catalytic membrane reactor (CMR) that couples CO splitting with methane oxidation reactions was constructed based on an oxygen-permeable perovskite asymmetric membrane. The asymmetric membrane comprises a dense SrFeTaO (SFT) separation layer and a porous Sr(FeTa)CuO (SFTC) catalytic layer. In the first stage reactor, a CO splitting reaction (CDS: 2CO→2CO+O) occurs at the SFTC catalytic layer. Subsequently, the O product is selectively extracted through the SFT separation layer to the permeated side for the methane combustion reaction (MCR), which provides an extremely low oxygen partial pressure to enhance the oxygen extraction. In the second stage, a Sr(FeTa)NiO (SFTN) catalyst is employed to reform the products derived from MCR. The two-stage CMR design results in a remarkable 35.4% CO conversion for CDS at 900 °C. The two-stage CMR was extended to a hollow fiber configuration combining with solar irradiation. The solar-assisted two-stage CMR can operate stably for over 50 hours with a high hydrogen yield of 18.1 mL min cm. These results provide a novel strategy for reducing CO emissions, suggesting potential avenues for the design of the high-performance CMRs and catalysts based on perovskite oxides in the future.
基于透氧包晶石非对称膜，构建了一种两级催化膜反应器（CMR），可将一氧化碳分离与甲烷氧化反应结合起来。不对称膜由致密的 SrFeTaO（SFT）分离层和多孔的 Sr（FeTa）CuO（SFTC）催化层组成。在第一级反应器中，SFTC 催化层发生 CO 分离反应（CDS：2CO→2CO+O）。随后，O 产物通过 SFT 分离层被选择性地萃取到渗透侧，进行甲烷燃烧反应（MCR），该反应提供了极低的氧分压，以提高氧气萃取率。在第二阶段，采用 Sr(FeTa)NiO (SFTN) 催化剂对 MCR 产生的产物进行重整。两段式 CMR 设计使 CDS 在 900 °C 下的 CO 转化率达到 35.4%。两级 CMR 扩展到中空纤维配置，并与太阳能照射相结合。太阳能辅助的双级 CMR 可稳定运行 50 小时以上，氢气产量高达 18.1 mL min cm。这些结果为减少一氧化碳排放提供了一种新的策略，为将来设计基于过氧化物氧化物的高性能 CMR 和催化剂提供了潜在的途径。
{"title":"Solar-assisted two-stage catalytic membrane reactor for coupling CO2 splitting with methane oxidation reaction","authors":"Jinkun Tan, Zhenbin Gu, Zhengkun Liu, Pei Wang, Reinout Meijboom, Guangru Zhang, Wanqin Jin","doi":"10.1016/j.gee.2024.07.006","DOIUrl":"https://doi.org/10.1016/j.gee.2024.07.006","url":null,"abstract":"A two-stage catalytic membrane reactor (CMR) that couples CO splitting with methane oxidation reactions was constructed based on an oxygen-permeable perovskite asymmetric membrane. The asymmetric membrane comprises a dense SrFeTaO (SFT) separation layer and a porous Sr(FeTa)CuO (SFTC) catalytic layer. In the first stage reactor, a CO splitting reaction (CDS: 2CO→2CO+O) occurs at the SFTC catalytic layer. Subsequently, the O product is selectively extracted through the SFT separation layer to the permeated side for the methane combustion reaction (MCR), which provides an extremely low oxygen partial pressure to enhance the oxygen extraction. In the second stage, a Sr(FeTa)NiO (SFTN) catalyst is employed to reform the products derived from MCR. The two-stage CMR design results in a remarkable 35.4% CO conversion for CDS at 900 °C. The two-stage CMR was extended to a hollow fiber configuration combining with solar irradiation. The solar-assisted two-stage CMR can operate stably for over 50 hours with a high hydrogen yield of 18.1 mL min cm. These results provide a novel strategy for reducing CO emissions, suggesting potential avenues for the design of the high-performance CMRs and catalysts based on perovskite oxides in the future.","PeriodicalId":12744,"journal":{"name":"Green Energy & Environment","volume":"134 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141779681","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Electrochemical reduction of CO is a promising approach to convert CO to high-valued chemicals and fuels. However, developing efficient electrocatalysts featuring desirable activity and selectivity is still a big challenge. In this work, a strategy of introducing functionalized molecules with desirable CO affinity to regulate Ag catalyst for promoting electrochemical reduction of CO was proposed. Specifically, 3-mercapto-1,2,4-triazole was introduced onto the Ag nanoparticle (Ag-m-Triz) for the first time to achieve selectively converting CO to carbon monoxide (CO). This Ag-m-Triz exhibits excellent performance for CO reduction with a high CO Faradaic efficiency (FE) of 99.2% and CO partial current density of 85.0 mA cm at −2.3 V vs. Ag/Ag in H-cell when combined with the ionic liquid-based electrolyte, 30 wt% 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][PF])-65 wt% acetonitrile (AcN)-5 wt% HO, which is 2.5-fold higher than the current density in Ag-powder under the same condition. Mechanism studies confirm that the significantly improved performance of Ag-m-Triz originates from (i) the stronger adsorption ability of CO molecule and (ii) the weaker binding energy to form the COOH∗ intermediate on the surface of Ag-m-Triz compared with the Ag-powder catalyst, which boosts the conversion of CO to CO. This research provides a facile way to regulate electrocatalysts for efficient CO reduction by introducing functionalized molecules.
一氧化碳的电化学还原是将一氧化碳转化为高价值化学品和燃料的一种前景广阔的方法。然而，开发具有理想活性和选择性的高效电催化剂仍是一项巨大挑战。在这项工作中，我们提出了一种将具有理想 CO 亲和性的官能化分子引入银催化剂的策略，以促进 CO 的电化学还原。具体而言，首次在银纳米粒子（Ag-m-Triz）上引入了 3-巯基-1,2,4-三唑，以实现将一氧化碳（CO）选择性地转化为一氧化碳（CO）。这种 Ag-m-Triz 在一氧化碳还原方面表现出色，一氧化碳法拉第效率 (FE) 高达 99.2%，一氧化碳部分电流密度为 85.0 mA cm，电压为 -2.3 V。当与离子液体型电解质（30 wt% 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][PF])-65 wt% acetonitrile (AcN)-5 wt% HO）结合使用时，在 H-cell 中的 Ag/Ag 部分电流密度为 85.0 mA cm，比相同条件下 Ag 粉末的电流密度高 2.5 倍。机理研究证实，Ag-m-Triz 性能的显著提高源于：(i) 与 Ag 粉末催化剂相比，Ag-m-Triz 对 CO 分子的吸附能力更强；(ii) 在 Ag-m-Triz 表面形成 COOH∗ 中间体的结合能更弱，从而促进了 CO 向 CO 的转化。这项研究提供了一种简便的方法，通过引入功能化分子来调节电催化剂，从而实现高效的 CO 还原。
{"title":"Boosting electrochemical reduction of CO2 to CO using molecule-regulated Ag nanoparticle in ionic liquids","authors":"Fangfang Li, Kuilin Peng, Chongyang Jiang, Shaojuan Zeng, Xiangping Zhang, Xiaoyan Ji","doi":"10.1016/j.gee.2024.07.005","DOIUrl":"https://doi.org/10.1016/j.gee.2024.07.005","url":null,"abstract":"Electrochemical reduction of CO is a promising approach to convert CO to high-valued chemicals and fuels. However, developing efficient electrocatalysts featuring desirable activity and selectivity is still a big challenge. In this work, a strategy of introducing functionalized molecules with desirable CO affinity to regulate Ag catalyst for promoting electrochemical reduction of CO was proposed. Specifically, 3-mercapto-1,2,4-triazole was introduced onto the Ag nanoparticle (Ag-m-Triz) for the first time to achieve selectively converting CO to carbon monoxide (CO). This Ag-m-Triz exhibits excellent performance for CO reduction with a high CO Faradaic efficiency (FE) of 99.2% and CO partial current density of 85.0 mA cm at −2.3 V vs. Ag/Ag in H-cell when combined with the ionic liquid-based electrolyte, 30 wt% 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][PF])-65 wt% acetonitrile (AcN)-5 wt% HO, which is 2.5-fold higher than the current density in Ag-powder under the same condition. Mechanism studies confirm that the significantly improved performance of Ag-m-Triz originates from (i) the stronger adsorption ability of CO molecule and (ii) the weaker binding energy to form the COOH∗ intermediate on the surface of Ag-m-Triz compared with the Ag-powder catalyst, which boosts the conversion of CO to CO. This research provides a facile way to regulate electrocatalysts for efficient CO reduction by introducing functionalized molecules.","PeriodicalId":12744,"journal":{"name":"Green Energy & Environment","volume":"414 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141779730","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-05DOI: 10.1016/j.gee.2024.07.002
Yanghe Fu, Yijing Gao, Huilin Jia, Yuncai Zhao, Yan Feng, Weidong Zhu, Fumin Zhang, Morris D. Argyle, Maohong Fan
Three large π-conjugated and imine-based COFs, named TFP-TAB, TFP-TTA, and TTA-TTB, were synthesized via the ordered incorporation of benzene and triazine rings in the same host framework to study how the structural units affect the efficiency of CO photoreduction. Results from both experiments and density-functional theory (DFT) calculations indicate the separation and transfer of the photoinduced charges is highly related to the triazine-N content and the conjugation degree in the skeletons of COFs. High-efficiency CO photoreduction can be achieved by rationally adjusting the number and position of both benzene and triazine rings in the COFs. Specifically, TTA-TTB, with orderly interlaced triazine-benzene heterojunctions, can suppress the recombination probability of electrons and holes, which effectively immobilizes the key species (COOH) and lowers the free energy change of the potential-determining step, and thus exhibits a superior visible-light-induced photocatalytic activity that yields 121.7 μmol HCOOH g h. This research, therefore, helps to elucidate the effects of the different structural blocks in COFs on inherent heterogeneous photocatalysis for CO reduction at a molecular level.
为了研究结构单元如何影响 CO 的光诱导效率，我们通过在同一宿主框架中有序地加入苯环和三嗪环的方法合成了三种大的π共轭和亚胺基 COF，分别命名为 TFP-TAB、TFP-TTA 和 TTA-TTB。实验和密度泛函理论（DFT）计算的结果表明，光诱导电荷的分离和转移与 COFs 骨架中三嗪-N 的含量和共轭度密切相关。通过合理调整 COF 中苯环和三嗪环的数量和位置，可以实现高效的 CO 光还原。具体来说，TTA-TTB 具有有序交错的三嗪-苯异质结，可以抑制电子和空穴的重组概率，从而有效地固定了关键物种（COOH），降低了电位决定步骤的自由能变化，因此表现出卓越的可见光诱导光催化活性，可产生 121.7 μmol HCOOH g h。因此，这项研究有助于从分子层面阐明 COFs 中不同结构单元对固有异相光催化还原 CO 的影响。
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LiPSCl is a highly wanted sulfide-solid-electrolyte (SSE) for developing all-solid-state lithium batteries, due to its high ionic conductivity, good processability and abundant compositional elements. However, its cyclability is poor because of harmful side reactions at the LiPSCl/Li interface and growth of lithium dendrites inside LiPSCl phase. Herein, we report a simple interface-engineering remedy to boost the electrochemical performance of LiPSCl, by coating its surface with a Li-compatible electrolyte LiOCl having low electronic conductivity. The obtained LiPSCl@LiOCl core@shell structure exhibits a synergistic effect. Consequently, compared with the bare LiPSCl, this composite electrolyte exhibits great performance improvements: 1) In Li|electrolyte|Li symmetric cells, the critical current density at 30 °C gets increased from 0.6 mA cm to 1.6 mA cm, and the lifetime gets prolonged from 320 h to 1400 h at the cycling current of 0.2 mA cm or from 6 h to 900 h at the cycling current of 0.5 mA cm; 2) In Li|electrolyte|NCM721 full cells running at 30 °C, the cycling capacity at 0.2 C (or 0.5 C) gets enhanced by 20% (or from unfeasible to be feasible) for 100 cycles and the rate capability reaches up to 2 C from 0.2 C; and in full cells running at 60 °C, the cycling capacity is increased by 7% at 0.2 C and the rate capability is enhanced to 3.0 C from 0.5 C. The experimental studies and theoretical computations show that the performance enhancements are due to the confined electron penetration and suppressed lithium dendrites growth at the LiPSCl@LiOCl interface.
由于具有高离子导电性、良好的可加工性和丰富的组成元素，LiPSCl 是开发全固态锂电池的理想硫化物-固体电解质（SSE）。然而，由于 LiPSCl/Li 界面的有害副反应以及 LiPSCl 相内锂枝晶的生长，其循环性较差。在此，我们报告了一种简单的界面工程补救方法，即在 LiPSCl 表面涂覆具有低电子传导性的锂兼容电解质 LiOCl，以提高其电化学性能。所获得的 LiPSCl@LiOCl 核@壳结构具有协同效应。因此，与裸 LiPSCl 相比，这种复合电解质的性能有了很大提高：1) 在锂|电解质|锂对称电池中，30 °C 时的临界电流密度从 0.6 mA cm 提高到 1.6 mA cm，循环电流为 0.2 mA cm 时的寿命从 320 h 延长到 1400 h，循环电流为 0.5 mA cm 时的寿命从 6 h 延长到 900 h；2) 在 30 °C 下运行的锂|电解质|NCM721 全电池中，0.2 C（或 0.实验研究和理论计算表明，性能的提高是由于在 LiPSCl@LiOCl 界面限制了电子的穿透并抑制了锂枝晶的生长。
{"title":"Synergistic Li6PS5Cl@Li3OCl composite electrolyte for high-performance all-solid-state lithium batteries","authors":"Yuzhe Zhang, Haolong Chang, Aiguo Han, Shijie Xu, Xinyu Wang, Shunjin Yang, Xiaohu Hu, Yujiang Sun, Xiao Sun, Xing Chen, Yongan Yang","doi":"10.1016/j.gee.2024.07.001","DOIUrl":"https://doi.org/10.1016/j.gee.2024.07.001","url":null,"abstract":"LiPSCl is a highly wanted sulfide-solid-electrolyte (SSE) for developing all-solid-state lithium batteries, due to its high ionic conductivity, good processability and abundant compositional elements. However, its cyclability is poor because of harmful side reactions at the LiPSCl/Li interface and growth of lithium dendrites inside LiPSCl phase. Herein, we report a simple interface-engineering remedy to boost the electrochemical performance of LiPSCl, by coating its surface with a Li-compatible electrolyte LiOCl having low electronic conductivity. The obtained LiPSCl@LiOCl core@shell structure exhibits a synergistic effect. Consequently, compared with the bare LiPSCl, this composite electrolyte exhibits great performance improvements: 1) In Li|electrolyte|Li symmetric cells, the critical current density at 30 °C gets increased from 0.6 mA cm to 1.6 mA cm, and the lifetime gets prolonged from 320 h to 1400 h at the cycling current of 0.2 mA cm or from 6 h to 900 h at the cycling current of 0.5 mA cm; 2) In Li|electrolyte|NCM721 full cells running at 30 °C, the cycling capacity at 0.2 C (or 0.5 C) gets enhanced by 20% (or from unfeasible to be feasible) for 100 cycles and the rate capability reaches up to 2 C from 0.2 C; and in full cells running at 60 °C, the cycling capacity is increased by 7% at 0.2 C and the rate capability is enhanced to 3.0 C from 0.5 C. The experimental studies and theoretical computations show that the performance enhancements are due to the confined electron penetration and suppressed lithium dendrites growth at the LiPSCl@LiOCl interface.","PeriodicalId":12744,"journal":{"name":"Green Energy & Environment","volume":"24 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141586146","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-29DOI: 10.1016/j.gee.2024.06.009
Yi Fang, Rui Ha, Jun Sun, Xue Liu, XiangDong Ding, WeiQun Shi
The separation of lithium isotopes (Li and Li) is of great importance for the nuclear industry. The lithium amalgam method is the only lithium isotopes separation process in industry, and the extensive use of mercury has raised concerns about its potential environmental hazards, which have prompted the search for more efficient and environmentally friendly alternatives. Crown ethers can bind lithium ions highly selectively and separate lithium isotopes effectively. A chemical exchange-based lithium isotopes separation method using crown ether decorated materials could be a viable and cost-effective alternative to the lithium amalgam method. In this review, we provide a systematic summary of the recent advances in lithium isotopes separation using crown ether decorated materials.
{"title":"Research progress on lithium isotopes separation by chemical exchange with crown ethers decorated materials","authors":"Yi Fang, Rui Ha, Jun Sun, Xue Liu, XiangDong Ding, WeiQun Shi","doi":"10.1016/j.gee.2024.06.009","DOIUrl":"https://doi.org/10.1016/j.gee.2024.06.009","url":null,"abstract":"The separation of lithium isotopes (Li and Li) is of great importance for the nuclear industry. The lithium amalgam method is the only lithium isotopes separation process in industry, and the extensive use of mercury has raised concerns about its potential environmental hazards, which have prompted the search for more efficient and environmentally friendly alternatives. Crown ethers can bind lithium ions highly selectively and separate lithium isotopes effectively. A chemical exchange-based lithium isotopes separation method using crown ether decorated materials could be a viable and cost-effective alternative to the lithium amalgam method. In this review, we provide a systematic summary of the recent advances in lithium isotopes separation using crown ether decorated materials.","PeriodicalId":12744,"journal":{"name":"Green Energy & Environment","volume":"23 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141586147","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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