Fascinatingly high saturation polarization and electric-field induced strain make bismuth sodium titanium (BNT) promising alternatives. Interestingly, significantly improved oxide-ion conductive capacity and ultrahigh asymmetric strain can be stimulated respectively, both of which show great sensitivity to the non-stoichiometry brought by either nominal acceptor dopant or intrinsic Bi volatilization. The weak bonded Bi-O covalency of the ferroelectrics plays an unexpected role in the multifunctional presentations. The highly polarized Bi ions configured with lone pair electrons contribute to the off-centering of the coordination environment and varied bond lengths. The inconspicuous structural change concerning the multifunctionality raises difficulty and necessity in recognizing the origin on both average and local. Herein, the structural evolution and defect form on the lattice level are elaborated including the oxygen-octahedral tilting, cations displacements, and their chemical environment by comparing with nominal oxygen-deficient composition. The impedance, polarization, and strain responses are discussed in detail to reveal the local polar distortions and average disorder for the non-cubic polytypes. The less symmetry of the spatial configurations and larger cations displacement are identified. Combined with the oxygen vacancy and defect dipole dynamics in the ferroelectric/strain/conductive performances, this work will arouse the interest of Bi-based ferroelectrics in the search for their multifunctional applications.
{"title":"Structural insight into the multifunctionality of non-stoichiometric BNT ferroelectrics","authors":"Jing Shi, Jicong Wang, Fangyuan Zhu, Wenchao Tian, Weibo Hua, Huiqing Fan, Jing Yang, Laijun Liu, Xiao Liu","doi":"10.1039/d4ta05841k","DOIUrl":"https://doi.org/10.1039/d4ta05841k","url":null,"abstract":"Fascinatingly high saturation polarization and electric-field induced strain make bismuth sodium titanium (BNT) promising alternatives. Interestingly, significantly improved oxide-ion conductive capacity and ultrahigh asymmetric strain can be stimulated respectively, both of which show great sensitivity to the non-stoichiometry brought by either nominal acceptor dopant or intrinsic Bi volatilization. The weak bonded Bi-O covalency of the ferroelectrics plays an unexpected role in the multifunctional presentations. The highly polarized Bi ions configured with lone pair electrons contribute to the off-centering of the coordination environment and varied bond lengths. The inconspicuous structural change concerning the multifunctionality raises difficulty and necessity in recognizing the origin on both average and local. Herein, the structural evolution and defect form on the lattice level are elaborated including the oxygen-octahedral tilting, cations displacements, and their chemical environment by comparing with nominal oxygen-deficient composition. The impedance, polarization, and strain responses are discussed in detail to reveal the local polar distortions and average disorder for the non-cubic polytypes. The less symmetry of the spatial configurations and larger cations displacement are identified. Combined with the oxygen vacancy and defect dipole dynamics in the ferroelectric/strain/conductive performances, this work will arouse the interest of Bi-based ferroelectrics in the search for their multifunctional applications.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"62 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642887","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xudong Qin, Haoran Tang, Haiyang Zhao, Lin Shao, Chunchen Liu, Lei Ying, Fei Huang
Covalent organic frameworks (COFs) exhibiting both high ion redox capability and high electronic conductivity show potential as cathode materials for Li-ion batteries (LIBs). Specifically, expanding the conjugation planes of the COF materials as well as incorporating redox-active groups can enhance their performance. Here, we developed a class of COF synthesis methods based on aldol condensation and realized the construction of fully conjugated conducting COF materials. In contrast to the majority of COFs synthesized through Schiff base reactions, COFs formed via aldol condensation feature interconnecting units joined by carbon–carbon double bonds. This structural characteristic results in an expanded conjugation plane, facilitating the synthesis of fully sp2-conjugated COFs, denoted as TBI-COF-O and TBI-COF-N. Notably, TBI-COF-O exhibits an electrical conductivity of 7.5 × 10−4 (±5 × 10−5) S cm−1 and a maximum capacity of 320 mA h g−1 at a discharge rate of 0.1C, which are among the highest values reported for COF-based LIBs. Moreover, TBI-COF-O based LIBs maintained 99.8% specific capacity even after 500 cycles, with 245 mA h g−1 at a discharge rate of 1C. This study further expands the variety of conjugated COFs and provides a new perspective on their use in energy storage.
{"title":"Fully conjugated covalent organic frameworks with high conductivity as superior cathode materials for Li-ion batteries","authors":"Xudong Qin, Haoran Tang, Haiyang Zhao, Lin Shao, Chunchen Liu, Lei Ying, Fei Huang","doi":"10.1039/d4ta05466k","DOIUrl":"https://doi.org/10.1039/d4ta05466k","url":null,"abstract":"Covalent organic frameworks (COFs) exhibiting both high ion redox capability and high electronic conductivity show potential as cathode materials for Li-ion batteries (LIBs). Specifically, expanding the conjugation planes of the COF materials as well as incorporating redox-active groups can enhance their performance. Here, we developed a class of COF synthesis methods based on aldol condensation and realized the construction of fully conjugated conducting COF materials. In contrast to the majority of COFs synthesized through Schiff base reactions, COFs formed <em>via</em> aldol condensation feature interconnecting units joined by carbon–carbon double bonds. This structural characteristic results in an expanded conjugation plane, facilitating the synthesis of fully sp<small><sup>2</sup></small>-conjugated COFs, denoted as <strong>TBI-COF-O</strong> and <strong>TBI-COF-N</strong>. Notably, <strong>TBI-COF-O</strong> exhibits an electrical conductivity of 7.5 × 10<small><sup>−4</sup></small> (±5 × 10<small><sup>−5</sup></small>) S cm<small><sup>−1</sup></small> and a maximum capacity of 320 mA h g<small><sup>−1</sup></small> at a discharge rate of 0.1C, which are among the highest values reported for COF-based LIBs. Moreover, <strong>TBI-COF-O</strong> based LIBs maintained 99.8% specific capacity even after 500 cycles, with 245 mA h g<small><sup>−1</sup></small> at a discharge rate of 1C. This study further expands the variety of conjugated COFs and provides a new perspective on their use in energy storage.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"246 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637613","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuxian Chen, Jiayi Rong, Qiaolin Fan, Meng Sun, Qiuyi Deng, Zhonghua Ni, Xiao Li, Tao Hu
Developing a cost-effective and commercially viable catalyst from non-noble metals that exhibits superior performance in both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) presents a significant challenge due to the distinct electrocatalytic mechanisms involved in each process. Herein, we engineered a three-dimensional, self-supporting heterostructure on carbon cloth (CC) using facile two-step electrodeposition, consisting of reduced graphene oxide (rGO) and cobalt sulfide (CoS), aimed at enhancing the efficiency of overall water electrolysis. The porous rGO network promoted the anchoring and vertical growth of CoS nanosheets, while the heterojunction between rGO and CoS enhanced the catalyst's stability remarkably. The CoS/rGO@CC catalyst exhibited extremely low overpotentials for both HER (η10=76.3 mV) and OER (η10=290.4 mV), maintaining these stable overpotentials for more than 24 hours, matching the performance of leading electrocatalysts based on noble metals. Moreover, by utilizing CoS/rGO@CC as both cathode and anode, we achieved overall water splitting with just 744 mV @10 mA cm-2. Theoretical calculations validated the synergistic effect of rGO and CoS nanosheets on enhancing HER and OER processes. Additionally, experimental data highlighted the CoS/rGO@CC catalyst's exceptional HER catalytic ability across varied pH levels, which provides a promising strategy to design low-cost and high-performance electrocatalysts for other energy-related applications.
由于氢进化反应（HER）和氧进化反应（OER）的电催化机理各不相同，因此从非贵金属中开发出一种在氢进化反应和氧进化反应中均表现出卓越性能的、具有成本效益和商业可行性的催化剂是一项重大挑战。在此，我们采用简便的两步电沉积法在碳布（CC）上设计了一种由还原氧化石墨烯（rGO）和硫化钴（CoS）组成的三维自支撑异质结构，旨在提高整体水电解效率。多孔的 rGO 网络促进了 CoS 纳米片的锚定和垂直生长，而 rGO 和 CoS 之间的异质结合则显著提高了催化剂的稳定性。CoS/rGO@CC 催化剂表现出极低的 HER（η10=76.3 mV）和 OER（η10=290.4 mV）过电位，这些稳定的过电位可维持 24 小时以上，与基于贵金属的领先电催化剂性能相当。此外，通过将 CoS/rGO@CC 同时用作阴极和阳极，我们实现了仅 744 mV @10 mA cm-2 的整体水分离。理论计算验证了 rGO 和 CoS 纳米片在增强 HER 和 OER 过程中的协同效应。此外，实验数据还突显了 CoS/rGO@CC 催化剂在不同 pH 值条件下卓越的 HER 催化能力，这为设计用于其他能源相关应用的低成本、高性能电催化剂提供了一种前景广阔的策略。
{"title":"Facile engineering of CoS/rGO heterostructures on carbon cloth for efficient all-pH hydrogen evolution reaction and alkaline water electrolysis","authors":"Yuxian Chen, Jiayi Rong, Qiaolin Fan, Meng Sun, Qiuyi Deng, Zhonghua Ni, Xiao Li, Tao Hu","doi":"10.1039/d4ta06710j","DOIUrl":"https://doi.org/10.1039/d4ta06710j","url":null,"abstract":"Developing a cost-effective and commercially viable catalyst from non-noble metals that exhibits superior performance in both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) presents a significant challenge due to the distinct electrocatalytic mechanisms involved in each process. Herein, we engineered a three-dimensional, self-supporting heterostructure on carbon cloth (CC) using facile two-step electrodeposition, consisting of reduced graphene oxide (rGO) and cobalt sulfide (CoS), aimed at enhancing the efficiency of overall water electrolysis. The porous rGO network promoted the anchoring and vertical growth of CoS nanosheets, while the heterojunction between rGO and CoS enhanced the catalyst's stability remarkably. The CoS/rGO@CC catalyst exhibited extremely low overpotentials for both HER (η10=76.3 mV) and OER (η10=290.4 mV), maintaining these stable overpotentials for more than 24 hours, matching the performance of leading electrocatalysts based on noble metals. Moreover, by utilizing CoS/rGO@CC as both cathode and anode, we achieved overall water splitting with just 744 mV @10 mA cm-2. Theoretical calculations validated the synergistic effect of rGO and CoS nanosheets on enhancing HER and OER processes. Additionally, experimental data highlighted the CoS/rGO@CC catalyst's exceptional HER catalytic ability across varied pH levels, which provides a promising strategy to design low-cost and high-performance electrocatalysts for other energy-related applications.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"9 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637610","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yongli Yang, Yadong Yu, Zhe Liu, Lijun Shang, Pan Xiang, Yu Xin, Tong Zhang, Zhonglu Guo, Mengyan Dai
Two-dimensional (2D) MA2Z4-based materials exhibit immense application potential in the fields of photocatalysis and optoelectronics due to their novel properties and interesting behaviors. But the practical applications of these 2D materials are limited by their undesirable recombination of photoexcited electrons and holes, poor optical absorption, low photoelectric conversion efficiency and redox driving force. Herein, we present material screening and design by using high-throughput first-principles calculations to accelerate the discovery of promising photovoltaic and photocatalytic candidates in the MA2Z4 family and their Janus structures. First of all, 61 thermodynamically, dynamically, and mechanically stable structures are screened out from 720 candidate structures. Thereafter, 37 of them exhibit semiconductor properties, and 14 of them have high carrier mobility and absorption performance. Moreover, for further application-driven screening, 10 and 2 potential candidates with high photovoltaic conversion efficiencies (PCE) and photocatalytic hydrogen evolution reaction (HER) activities are selected, respectively. Finally, the regulation law and intrinsic mechanism of asymmetric Janus structures on physicochemical properties of MA2Z4 are elucidated. We believe that our study will provide a theoretical foundation and innovative insights for the design of novel Janus structures and their applications in the fields of optoelectronics and photocatalysis.
{"title":"High-throughput computational screening of novel MA2Z4-type Janus structures with excellent photovoltaic and photocatalytic properties","authors":"Yongli Yang, Yadong Yu, Zhe Liu, Lijun Shang, Pan Xiang, Yu Xin, Tong Zhang, Zhonglu Guo, Mengyan Dai","doi":"10.1039/d4ta07195f","DOIUrl":"https://doi.org/10.1039/d4ta07195f","url":null,"abstract":"Two-dimensional (2D) MA<small><sub>2</sub></small>Z<small><sub>4</sub></small>-based materials exhibit immense application potential in the fields of photocatalysis and optoelectronics due to their novel properties and interesting behaviors. But the practical applications of these 2D materials are limited by their undesirable recombination of photoexcited electrons and holes, poor optical absorption, low photoelectric conversion efficiency and redox driving force. Herein, we present material screening and design by using high-throughput first-principles calculations to accelerate the discovery of promising photovoltaic and photocatalytic candidates in the MA<small><sub>2</sub></small>Z<small><sub>4</sub></small> family and their Janus structures. First of all, 61 thermodynamically, dynamically, and mechanically stable structures are screened out from 720 candidate structures. Thereafter, 37 of them exhibit semiconductor properties, and 14 of them have high carrier mobility and absorption performance. Moreover, for further application-driven screening, 10 and 2 potential candidates with high photovoltaic conversion efficiencies (PCE) and photocatalytic hydrogen evolution reaction (HER) activities are selected, respectively. Finally, the regulation law and intrinsic mechanism of asymmetric Janus structures on physicochemical properties of MA<small><sub>2</sub></small>Z<small><sub>4</sub></small> are elucidated. We believe that our study will provide a theoretical foundation and innovative insights for the design of novel Janus structures and their applications in the fields of optoelectronics and photocatalysis.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"45 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610091","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Architecting efficient, multifunctional, and low-cost nano-electrocatalysts plays a vital role in electrochemical energy conversion and storage systems. Low-Pt hybrid catalysts are in high demand, offering cost-effective solutions for electrode materials in direct methanol fuel cells and Zn-air batteries. Herein, we synthesized a ternary nanocomposite (PtNP-ZnO@CQDs) composed of ultrafine platinum nanoparticles (PtNPs) of below 5 nm on photosensitive ZnO and carbon quantum dots (CQDs) via a simple one-pot hydrothermal process for efficient photoinduced electrocatalytic methanol oxidation reaction (MOR), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) with commendable durability. Comprehensive characterizations through XRD, FT-IR, XPS, BET, SEM, EDX, and HRTEM confirm the nanocomposite's structure and properties. The catalyst attains a MOR current density of 9.1 mA cm-2 in photoinduced electrocatalytic methanol oxidation with high CO tolerance and durability. During OER, the PtNP-ZnO@CQDs catalyst reveals a lower overpotential than the commercial RuO2 at higher current densities over 30 mA cm-2. In ORR, the catalyst showed a higher half-wave potential of 0.96 V, higher limiting current density, mass activity, and chronoamperometric stability than the commercial Pt/C used as a standard here. The PtNP-ZnO@CQDs also exhibited low peroxide yield, a high number of electron transfers, and photoinduced ORR capability, indicating its superiority over commercial Pt/C catalysts. When used in a rechargeable aqueous zinc-air battery (ZAB), the PtNP-ZnO@CQDs air cathode delivered an open circuit potential of 1.55 V with an impressive energy density of 668 Wh/kg and a specific capacity of 532 mAh/g, outperforming ZABs with commercial Pt/C and RuO2. Interestingly, the ZAB composed of PtNP-ZnO@CQDs air cathode shows outstanding long-term cycle stability, maintaining the round trip efficiency of 66.87% after 60 h. The assembled ZABs in series successfully powered LED panels, demonstrating the potential of this low-cost, bifunctional Pt-based electrocatalyst for future ZAB commercialization.
构建高效、多功能、低成本的纳米电催化剂在电化学能量转换和储存系统中发挥着至关重要的作用。低铂混合催化剂需求量很大，可为直接甲醇燃料电池和锌-空气电池的电极材料提供具有成本效益的解决方案。在此，我们通过简单的一锅水热法合成了一种三元纳米复合材料（PtNP-ZnO@CQDs），该复合材料由5纳米以下的超细铂纳米颗粒（PtNPs）和光敏氧化锌（ZnO）以及碳量子点（CQDs）组成，可用于高效的光诱导电催化甲醇氧化反应（MOR）、氧进化反应（OER）和氧还原反应（ORR），并具有良好的耐久性。通过 XRD、FT-IR、XPS、BET、SEM、EDX 和 HRTEM 进行的全面表征证实了纳米复合材料的结构和特性。该催化剂在光诱导电催化甲醇氧化过程中可达到 9.1 mA cm-2 的 MOR 电流密度，并具有较高的 CO 容忍性和耐久性。在 OER 过程中，PtNP-ZnO@CQDs 催化剂在超过 30 mA cm-2 的较高电流密度下，过电位低于商用 RuO2。在 ORR 中，该催化剂显示出 0.96 V 的较高半波电位、较高的极限电流密度、质量活性以及计时器稳定性，均优于此处用作标准的商用 Pt/C。PtNP-ZnO@CQDs 还表现出较低的过氧化物产率、较高的电子转移次数和光诱导 ORR 能力，表明其优于商用 Pt/C 催化剂。当用于可充电锌空气水电池（ZAB）时，PtNP-ZnO@CQDs 空气阴极的开路电位为 1.55 V，能量密度高达 668 Wh/kg，比容量为 532 mAh/g，优于使用商用 Pt/C 和 RuO2 的 ZAB。有趣的是，由 PtNP-ZnO@CQDs 空气阴极组成的 ZAB 显示出出色的长期循环稳定性，在 60 小时后仍能保持 66.87% 的往返效率。
{"title":"Pt-Nanoparticles on ZnO/Carbon Quantum Dots: A Trifunctional Nanocomposite with Superior Electrocatalytic Activity Bosting Direct Methanol Fuel Cell and Zinc-Air Battery","authors":"Anup Kumar Pradhan, Sayan Halder, Chanchal Chakraborty","doi":"10.1039/d4ta05630b","DOIUrl":"https://doi.org/10.1039/d4ta05630b","url":null,"abstract":"Architecting efficient, multifunctional, and low-cost nano-electrocatalysts plays a vital role in electrochemical energy conversion and storage systems. Low-Pt hybrid catalysts are in high demand, offering cost-effective solutions for electrode materials in direct methanol fuel cells and Zn-air batteries. Herein, we synthesized a ternary nanocomposite (PtNP-ZnO@CQDs) composed of ultrafine platinum nanoparticles (PtNPs) of below 5 nm on photosensitive ZnO and carbon quantum dots (CQDs) via a simple one-pot hydrothermal process for efficient photoinduced electrocatalytic methanol oxidation reaction (MOR), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) with commendable durability. Comprehensive characterizations through XRD, FT-IR, XPS, BET, SEM, EDX, and HRTEM confirm the nanocomposite's structure and properties. The catalyst attains a MOR current density of 9.1 mA cm-2 in photoinduced electrocatalytic methanol oxidation with high CO tolerance and durability. During OER, the PtNP-ZnO@CQDs catalyst reveals a lower overpotential than the commercial RuO2 at higher current densities over 30 mA cm-2. In ORR, the catalyst showed a higher half-wave potential of 0.96 V, higher limiting current density, mass activity, and chronoamperometric stability than the commercial Pt/C used as a standard here. The PtNP-ZnO@CQDs also exhibited low peroxide yield, a high number of electron transfers, and photoinduced ORR capability, indicating its superiority over commercial Pt/C catalysts. When used in a rechargeable aqueous zinc-air battery (ZAB), the PtNP-ZnO@CQDs air cathode delivered an open circuit potential of 1.55 V with an impressive energy density of 668 Wh/kg and a specific capacity of 532 mAh/g, outperforming ZABs with commercial Pt/C and RuO2. Interestingly, the ZAB composed of PtNP-ZnO@CQDs air cathode shows outstanding long-term cycle stability, maintaining the round trip efficiency of 66.87% after 60 h. The assembled ZABs in series successfully powered LED panels, demonstrating the potential of this low-cost, bifunctional Pt-based electrocatalyst for future ZAB commercialization.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"12 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637615","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kai Wu, Pengwei Yang, Shuaijun Fan, Yifan Wu, Jingxiang Ma, Lijuan Yang, Hongtao Zhu, Xiaoying Ma, Heli Gao, Wentong Chen, Jun Jia, Shuangchen Ma
The recycling of industrially emitted CO2 is an urgent environmental task. Electrochemical reduction of CO2 into valuable chemical products presents an attractive approach. However, due to the inherent high chemical stability of CO2 molecules and the complex sequence of multiple electron and proton transfer steps involved in the CO2 reduction reaction (CO2RR), current electrocatalytic systems commonly face challenges such as low CO2 conversion rates and energy utilization efficiency, limited current density, and short electrode lifespan. Herein, we adopt a simple three-step process involving in situ chemical etching, thermal oxidation, and electrochemical reduction to construct bismuth nanosheets (Bi NSs) with abundant lattice dislocations on copper foam, and introduce nanobubble technology to enhance the CO2RR process. In an H-type cell with flowing electrolyte, our Bi NSs/CF electrode achieved a remarkable formate Faradaic efficiency (FEFormate) of 95.36% at a low applied potential of -1.08 V vs. RHE (reversible hydrogen electrode), along with a significant formate partial current density (JFormate) of ~38 mA cm-2 and an energy efficiency of ~60%. Even within a wider operating window (-0.78 to -1.18 V), the FEFormate remained at a high level (>91%). Importantly, the application of nanobubble technology made the CO2 conversion rate increase nearly fivefold. Further density functional theory calculations confirmed that the Bi NSs with lattice dislocations on the Bi NSs/CF surface can effectively stabilize the *OCHO intermediate, thereby achieving high activity and selectivity for CO2RR. This work highlights the significant roles of nanobubble technology, size-dependent catalysis, and crystal defect engineering strategies in the field of electrocatalysis, elucidating the activity sources of the developed catalyst in the electrochemical CO2 reduction process, and providing valuable insights for the design and development of high-performance electrocatalytic systems for CO2RR and other fields.
回收利用工业排放的二氧化碳是一项紧迫的环保任务。用电化学方法将二氧化碳还原成有价值的化学产品是一种极具吸引力的方法。然而，由于二氧化碳分子固有的高化学稳定性以及二氧化碳还原反应（CO2RR）中涉及的多个电子和质子转移步骤的复杂顺序，目前的电催化系统普遍面临着二氧化碳转化率和能量利用效率低、电流密度有限以及电极寿命短等挑战。在此，我们采用原位化学蚀刻、热氧化和电化学还原的简单三步法，在泡沫铜上构建出具有丰富晶格位错的纳米铋片（Bi NSs），并引入纳米气泡技术来增强 CO2RR 过程。在带有流动电解质的 H 型电池中，我们的 Bi NSs/CF 电极在相对于 RHE（可逆氢电极）-1.08 V 的低应用电位下实现了 95.36% 的显著甲酸法拉第效率 (FEFormate)，以及约 38 mA cm-2 的显著甲酸部分电流密度 (JFormate) 和约 60% 的能量效率。即使在更宽的操作窗口（-0.78 至 -1.18 V）内，甲酸盐部分电流密度仍保持在较高水平（91%）。重要的是，纳米气泡技术的应用使二氧化碳转化率提高了近五倍。进一步的密度泛函理论计算证实，在 Bi NSs/CF 表面具有晶格位错的 Bi NSs 能有效稳定 *OCHO 中间体，从而实现 CO2RR 的高活性和高选择性。这项工作凸显了纳米气泡技术、尺寸依赖催化和晶体缺陷工程策略在电催化领域的重要作用，阐明了所开发催化剂在电化学 CO2 还原过程中的活性来源，为 CO2RR 及其他领域高性能电催化系统的设计和开发提供了宝贵的启示。
{"title":"Formation of Bismuth Nanosheets on Copper Foam Coupled with Nanobubble Technology for Enhanced Electrocatalytic CO2 Reduction","authors":"Kai Wu, Pengwei Yang, Shuaijun Fan, Yifan Wu, Jingxiang Ma, Lijuan Yang, Hongtao Zhu, Xiaoying Ma, Heli Gao, Wentong Chen, Jun Jia, Shuangchen Ma","doi":"10.1039/d4ta06898j","DOIUrl":"https://doi.org/10.1039/d4ta06898j","url":null,"abstract":"The recycling of industrially emitted CO2 is an urgent environmental task. Electrochemical reduction of CO2 into valuable chemical products presents an attractive approach. However, due to the inherent high chemical stability of CO2 molecules and the complex sequence of multiple electron and proton transfer steps involved in the CO2 reduction reaction (CO2RR), current electrocatalytic systems commonly face challenges such as low CO2 conversion rates and energy utilization efficiency, limited current density, and short electrode lifespan. Herein, we adopt a simple three-step process involving in situ chemical etching, thermal oxidation, and electrochemical reduction to construct bismuth nanosheets (Bi NSs) with abundant lattice dislocations on copper foam, and introduce nanobubble technology to enhance the CO2RR process. In an H-type cell with flowing electrolyte, our Bi NSs/CF electrode achieved a remarkable formate Faradaic efficiency (FEFormate) of 95.36% at a low applied potential of -1.08 V vs. RHE (reversible hydrogen electrode), along with a significant formate partial current density (JFormate) of ~38 mA cm-2 and an energy efficiency of ~60%. Even within a wider operating window (-0.78 to -1.18 V), the FEFormate remained at a high level (>91%). Importantly, the application of nanobubble technology made the CO2 conversion rate increase nearly fivefold. Further density functional theory calculations confirmed that the Bi NSs with lattice dislocations on the Bi NSs/CF surface can effectively stabilize the *OCHO intermediate, thereby achieving high activity and selectivity for CO2RR. This work highlights the significant roles of nanobubble technology, size-dependent catalysis, and crystal defect engineering strategies in the field of electrocatalysis, elucidating the activity sources of the developed catalyst in the electrochemical CO2 reduction process, and providing valuable insights for the design and development of high-performance electrocatalytic systems for CO2RR and other fields.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"21 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637616","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Developing a new generation of increased energy, stability, and easily applicable N-rich energetic materials to replace RDX and HMX has posed significant challenges over the past decade. This work presents the design and synthesis of a series of novel N-rich energetic materials (N1 to N3 series) based on the triazole–tetrazole system. Among these, the N3 series demonstrates exceptional detonation performance and stability. It is noteworthy that the N3-3 molecule has achieved the best overall performance among N-rich energetic materials, with an onset decomposition temperature of 302 °C and a detonation velocity of 9341 m s−1, which significantly surpasses that of HMX. Additionally, structural studies of the N1 molecule reveal that the positioning effect of the nitro group and steric hindrance within the molecule disrupt the planar characteristics of the triazole–tetrazole system. In contrast, the amino group in the N3 series enhances molecular planarity, facilitating the formation of large conjugated systems and extensive hydrogen bond networks in N-rich energetic materials. This approach effectively enhances the stability of energetic material molecules and offers valuable insights for the development and design of stable N-rich energetic compounds.
过去十年来，开发新一代能量更高、更稳定、更易于应用的富 N 高能材料以取代 RDX 和 HMX 一直是一项重大挑战。本研究以三唑-四唑体系为基础，设计并合成了一系列新型富 N 高能材料（N1 至 N3 系列）。其中，N3 系列具有优异的引爆性能和稳定性。值得注意的是，N3-3 分子的起爆分解温度为 302 ℃，起爆速度为 9341 m s-1，大大超过了 HMX，是富 N 高能材料中综合性能最好的。此外，对 N1 分子的结构研究表明，硝基的定位效应和分子内的立体阻碍破坏了三唑-四唑体系的平面特性。相反，N3 系列中的氨基增强了分子的平面性，有利于在富含 N 的高能材料中形成大型共轭体系和广泛的氢键网络。这种方法有效提高了高能材料分子的稳定性，为开发和设计稳定的富 N 高能化合物提供了宝贵的启示。
{"title":"Towards advanced N-rich energetic explosives: based on tetrazole and triazole groups with large conjugated systems and extensive hydrogen bonds","authors":"Guofeng Zhang, Xue Hao, Yongbin Zou, Shichang Liu, Junjie Wei, Zhen Dong, Zhiwen Ye","doi":"10.1039/d4ta06447j","DOIUrl":"https://doi.org/10.1039/d4ta06447j","url":null,"abstract":"Developing a new generation of increased energy, stability, and easily applicable N-rich energetic materials to replace RDX and HMX has posed significant challenges over the past decade. This work presents the design and synthesis of a series of novel N-rich energetic materials (<strong>N1</strong> to <strong>N3</strong> series) based on the triazole–tetrazole system. Among these, the <strong>N3</strong> series demonstrates exceptional detonation performance and stability. It is noteworthy that the <strong>N3-3</strong> molecule has achieved the best overall performance among N-rich energetic materials, with an onset decomposition temperature of 302 °C and a detonation velocity of 9341 m s<small><sup>−1</sup></small>, which significantly surpasses that of HMX. Additionally, structural studies of the <strong>N1</strong> molecule reveal that the positioning effect of the nitro group and steric hindrance within the molecule disrupt the planar characteristics of the triazole–tetrazole system. In contrast, the amino group in the <strong>N3</strong> series enhances molecular planarity, facilitating the formation of large conjugated systems and extensive hydrogen bond networks in N-rich energetic materials. This approach effectively enhances the stability of energetic material molecules and offers valuable insights for the development and design of stable N-rich energetic compounds.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"7 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610577","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yin-Ying Ting, Ben Breitung, Simon Schweidler, Junbo Wang, Michael Eikerling, Piotr M. Kowalski, Olivier Guillon, Payam Kaghazchi
Li-rich layered oxides can potentially provide high capacity, thereby enhancing energy density as cathode materials in Li-ion batteries. However, one of the main drawbacks is their low cycling stability. It has been proposed that the structural stability of a solid solution compound might be enhanced by exploiting the high-entropy concept. Here, we studied two Li-rich layered oxide cathode materials with multiple cations in their transition metal sites, categorized as medium or high entropy: Li(Li0.2Co0.18Ni0.18Mn0.44)O2 and Li(Li0.2Co0.18Ni0.18Mn0.18Ti0.26)O2. The synthesized materials, however, experienced a large capacity loss during the first charge/discharge cycle. We performed first-principles calculations to understand the mechanism behind the capacity fading and discovered significant structural changes in both systems. Specifically, we observed extensive Li/Ni interchange, migration of transition metal ions to Li sites, and formation of secondary phases. For the Ti-containing material, which shows a larger capacity fade than the other system, we even observed the formation of a spinel phase. The computed enthalpies of secondary phase formation reactions exhibit large negative values. However, the estimated (maximum) configurational entropy contributions to the free energies of these reactions are much smaller and therefore not determining factors. This study provides crucial insights into degradation mechanisms in Li-rich high-entropy systems, aiding the future design and development of advanced cathode materials for next-generation lithium-ion batteries.
富锂层状氧化物作为锂离子电池的阴极材料，有可能提供高容量，从而提高能量密度。然而，其主要缺点之一是循环稳定性较低。有人提出，可以通过利用高熵概念来增强固溶体化合物的结构稳定性。在此，我们研究了两种富含锂的层状氧化物阴极材料，它们的过渡金属位点中含有多个阳离子，被归类为中熵或高熵：Li(Li0.2Co0.18Ni0.18Mn0.44)O2 and Li(Li0.2Co0.18Ni0.18Mn0.18Ti0.26)O2.然而，合成的材料在第一个充放电周期中出现了较大的容量损失。我们进行了第一原理计算，以了解容量衰减背后的机理，并发现这两种体系都发生了显著的结构变化。具体来说，我们观察到了广泛的锂/镍交换、过渡金属离子向锂位迁移以及次生相的形成。含钛材料的容量衰减比其他体系更大，我们甚至观察到尖晶石相的形成。计算得出的次生相形成反应焓呈现较大的负值。然而，这些反应的自由能的估计（最大）构型熵贡献要小得多，因此不是决定性因素。这项研究为富锂高熵体系的降解机制提供了重要见解，有助于未来新一代锂离子电池先进正极材料的设计和开发。
{"title":"Delithiation-induced secondary phase formation in Li-rich cathode materials","authors":"Yin-Ying Ting, Ben Breitung, Simon Schweidler, Junbo Wang, Michael Eikerling, Piotr M. Kowalski, Olivier Guillon, Payam Kaghazchi","doi":"10.1039/d4ta06030j","DOIUrl":"https://doi.org/10.1039/d4ta06030j","url":null,"abstract":"Li-rich layered oxides can potentially provide high capacity, thereby enhancing energy density as cathode materials in Li-ion batteries. However, one of the main drawbacks is their low cycling stability. It has been proposed that the structural stability of a solid solution compound might be enhanced by exploiting the high-entropy concept. Here, we studied two Li-rich layered oxide cathode materials with multiple cations in their transition metal sites, categorized as medium or high entropy: Li(Li<small><sub>0.2</sub></small>Co<small><sub>0.18</sub></small>Ni<small><sub>0.18</sub></small>Mn<small><sub>0.44</sub></small>)O<small><sub>2</sub></small> and Li(Li<small><sub>0.2</sub></small>Co<small><sub>0.18</sub></small>Ni<small><sub>0.18</sub></small>Mn<small><sub>0.18</sub></small>Ti<small><sub>0.26</sub></small>)O<small><sub>2</sub></small>. The synthesized materials, however, experienced a large capacity loss during the first charge/discharge cycle. We performed first-principles calculations to understand the mechanism behind the capacity fading and discovered significant structural changes in both systems. Specifically, we observed extensive Li/Ni interchange, migration of transition metal ions to Li sites, and formation of secondary phases. For the Ti-containing material, which shows a larger capacity fade than the other system, we even observed the formation of a spinel phase. The computed enthalpies of secondary phase formation reactions exhibit large negative values. However, the estimated (maximum) configurational entropy contributions to the free energies of these reactions are much smaller and therefore not determining factors. This study provides crucial insights into degradation mechanisms in Li-rich high-entropy systems, aiding the future design and development of advanced cathode materials for next-generation lithium-ion batteries.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"35 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610090","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nanping Deng, Yilong Wang, Qiang Zeng, Yang Feng, Gang Wang, Hao Chi, Weimin Kang, Bowen Cheng
Highly efficiency, excellent stability and low-cost catalysts equipping with uniform distribution and enough active sites are rather important for zinc-air batteries (ZABs). In this study, inspired by hollow bubble structured carbon materials and heterostructure characteristics, the hierarchically porous carbon nanofibers with 3D network structure including heterojunction FeCu/FeF3 active nanoparticles and enriched N, F co-doping (FeCu/FeF3@HPCNFs) are prepared for oxygen reduction/evolution reaction (ORR/OER). The hierarchically porous structure inside the nanofibers combining with the hollow bubble structured carbon outside the nanofibers together can increase the specific surface area and carbon edge defects of the composite materials, thus effectively accelerating mass transfer at three-phase interfaces. Meanwhile, the heterojunction FeCu/FeF3 and unique heteroatoms co-doping can reduce charge transport resistance and accelerate catalytic reaction rate. Thus the FeCu/FeF3@HPCNFs display exceedingly good electrocatalytic performance for ORR (EORR, 1/2 = 0.87 V vs. RHE) and OER (ηOER, 10 = 377 mV at 10 mA cm−2). More importantly, both the aqueous rechargeable ZABs and flexible foldable solid-state ZABs assembled with the FeCu/FeF3@HPCNFs catalyst reveal a outstanding maximum power density and excellent long-term cycling stability. In addition, the theoretical analysis also reveals the FeCu/FeF3@HPCNFs electrocatalyst can reasonably adjust the electron distribution, effectively lower the reaction barrier of intermediate and greatly reduce OER/ORR overpotential. All in all, the work will open up a new avenue for facile construction of highly active, structurally stable and cost-effective bi-functional catalysts for ZABs.
具有均匀分布和足够活性位点的高效率、高稳定性和低成本催化剂对于锌空气电池（ZAB）而言相当重要。本研究受空心气泡结构碳材料和异质结构特点的启发，制备了具有三维网络结构的分层多孔碳纳米纤维，其中包括异质结合的 FeCu/FeF3 活性纳米颗粒和富含 N、F 的共掺杂（FeCu/FeF3@HPCNFs），用于氧还原/进化反应（ORR/OER）。纳米纤维内部的分层多孔结构与纳米纤维外部的中空气泡结构碳相结合，可增加复合材料的比表面积和碳边缘缺陷，从而有效加速三相界面的传质。同时，FeCu/FeF3 的异质结和独特的杂原子共掺杂可以降低电荷传输阻力，加快催化反应速率。因此，FeCu/FeF3@HPCNFs 在 ORR（EORR，1/2 = 0.87 V vs. RHE）和 OER（ηOER，10 = 377 mV，10 mA cm-2）方面表现出了极好的电催化性能。更重要的是，使用 FeCu/FeF3@HPCNFs 催化剂组装的水性可充电 ZAB 和柔性可折叠固态 ZAB 都具有出色的最大功率密度和长期循环稳定性。此外，理论分析还表明，FeCu/FeF3@HPCNFs 电催化剂能合理调节电子分布，有效降低中间反应势垒，大大降低 OER/ORR 过电位。总之，这项工作将为简便地构建高活性、结构稳定和经济高效的 ZAB 双功能催化剂开辟一条新途径。
{"title":"Facile construction of hierarchically porous carbon nanofibers modified by FeCu/FeF3 heterojunction for oxygen electrocatalysis in liquid and flexible Zn-air batteries","authors":"Nanping Deng, Yilong Wang, Qiang Zeng, Yang Feng, Gang Wang, Hao Chi, Weimin Kang, Bowen Cheng","doi":"10.1039/d4ta05503a","DOIUrl":"https://doi.org/10.1039/d4ta05503a","url":null,"abstract":"Highly efficiency, excellent stability and low-cost catalysts equipping with uniform distribution and enough active sites are rather important for zinc-air batteries (ZABs). In this study, inspired by hollow bubble structured carbon materials and heterostructure characteristics, the hierarchically porous carbon nanofibers with 3D network structure including heterojunction FeCu/FeF3 active nanoparticles and enriched N, F co-doping (FeCu/FeF3@HPCNFs) are prepared for oxygen reduction/evolution reaction (ORR/OER). The hierarchically porous structure inside the nanofibers combining with the hollow bubble structured carbon outside the nanofibers together can increase the specific surface area and carbon edge defects of the composite materials, thus effectively accelerating mass transfer at three-phase interfaces. Meanwhile, the heterojunction FeCu/FeF3 and unique heteroatoms co-doping can reduce charge transport resistance and accelerate catalytic reaction rate. Thus the FeCu/FeF3@HPCNFs display exceedingly good electrocatalytic performance for ORR (EORR, 1/2 = 0.87 V vs. RHE) and OER (ηOER, 10 = 377 mV at 10 mA cm−2). More importantly, both the aqueous rechargeable ZABs and flexible foldable solid-state ZABs assembled with the FeCu/FeF3@HPCNFs catalyst reveal a outstanding maximum power density and excellent long-term cycling stability. In addition, the theoretical analysis also reveals the FeCu/FeF3@HPCNFs electrocatalyst can reasonably adjust the electron distribution, effectively lower the reaction barrier of intermediate and greatly reduce OER/ORR overpotential. All in all, the work will open up a new avenue for facile construction of highly active, structurally stable and cost-effective bi-functional catalysts for ZABs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"73 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610092","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Muhammad Muzakir, Karnan Manickavasakam, Eric Jianfeng Cheng, Fangling Yang, Ziyun Wang, Hao Li, Xinyu Zhang, Jiaqian Qin
The development of fast synthesis methods and accurate engineering of the shapes and characteristics of inorganic solid electrolytes has been substantially aided by the advancement of science and technology in electrolyte engineering. The goal of this development is to meet the strict requirements for high-performance ASSBs, or all-solid-state batteries. The synthesis methods and electrochemical characteristics of inorganic solid electrolytes (ISEs), such as NASICON-based oxide, sulfide, hydroborate, anti-perovskite, and halide, as well as their uses in ASSBs, are covered in this review along with recent discoveries. ASSB problems, such as poor ISE-electrode compatibility and the potential for adverse reactions at the electrode interface, may be resolved by using ISEs in composite cathodes and solid interface layers. This illustrates the variety of applications for the ISEs class in the creation of complex ASSB models. In conclusion, we showcase existing ASSB models and forthcoming tactics to advance the advancement of ASSB development for the next generation.
电解质工程科学和技术的发展极大地推动了无机固体电解质快速合成方法和精确形状与特性工程学的发展。这一发展的目标是满足对高性能 ASSB 或全固态电池的严格要求。本综述将介绍无机固态电解质（ISE）的合成方法和电化学特性，如基于 NASICON 的氧化物、硫化物、硼酸盐、反透镜石和卤化物，以及它们在 ASSB 中的用途和最新发现。通过在复合阴极和固体界面层中使用 ISE，可以解决 ASSB 存在的问题，如 ISE 与电极的兼容性差以及电极界面可能发生不良反应。这说明了 ISE 类在创建复杂 ASSB 模型中的各种应用。最后，我们展示了现有的 ASSB 模型和即将推出的策略，以推动下一代 ASSB 的发展。
{"title":"Inorganic solid electrolytes for all-solid-state sodium/lithium-ion batteries: recent development and applications","authors":"Muhammad Muzakir, Karnan Manickavasakam, Eric Jianfeng Cheng, Fangling Yang, Ziyun Wang, Hao Li, Xinyu Zhang, Jiaqian Qin","doi":"10.1039/d4ta06117a","DOIUrl":"https://doi.org/10.1039/d4ta06117a","url":null,"abstract":"The development of fast synthesis methods and accurate engineering of the shapes and characteristics of inorganic solid electrolytes has been substantially aided by the advancement of science and technology in electrolyte engineering. The goal of this development is to meet the strict requirements for high-performance ASSBs, or all-solid-state batteries. The synthesis methods and electrochemical characteristics of inorganic solid electrolytes (ISEs), such as NASICON-based oxide, sulfide, hydroborate, anti-perovskite, and halide, as well as their uses in ASSBs, are covered in this review along with recent discoveries. ASSB problems, such as poor ISE-electrode compatibility and the potential for adverse reactions at the electrode interface, may be resolved by using ISEs in composite cathodes and solid interface layers. This illustrates the variety of applications for the ISEs class in the creation of complex ASSB models. In conclusion, we showcase existing ASSB models and forthcoming tactics to advance the advancement of ASSB development for the next generation.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"22 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：