Monochloroacetic acid (MCAA) is identified as a highly carcinogenic disinfection by-product in chlorinated drinking water. In this study, a series of CeO2-supported Pd catalysts (Pd/MCeO2) were synthesized through one-step calcination of Pd-loaded Ce-UiO-66-BDC (Ce-MOF), and the liquid-phase catalytic hydrodechlorination of MCAA was explored using these catalysts. For comparison, Pd/CeO2 catalysts were additionally synthesized using the conventional impregnation method. The characterization results reveal that the catalysts exhibit strong metal–support interaction, leading to high Pd dispersion and Pdn+ content. Additionally, the calcination temperature significantly influences catalytic performance, with the catalyst calcined at 500 °C (Pd/MCeO2-500) demonstrating the highest catalytic activity and achieving complete dechlorination of MCAA within 50 min. Furthermore, it is found that the catalytic MCAA hydrodechlorination using the catalysts adheres to the Langmuir–Hinshelwood model. Accordingly, low reaction pH is favorable for the catalytic hydrodechlorination of MCAA, enhancing MCAA adsorption on the catalyst surface due to the electrostatic interaction between MCAA and the catalyst surface. Theoretical results suggest that the presence of Pdn+ efficiently facilitates MCAA adsorption and C–Cl cleavage, thus significantly enhancing the liquid-phase catalytic hydrodechlorination.
{"title":"Synergy of metal–support interaction and positive Pd species promoting efficient C–Cl bond activation on Pd-based Ce-MOF-derived catalysts","authors":"Xiao-Jie Hu, Yu-Han Sun, Ling-Yue Liu, Dan-Jun Mao, Shou-Rong Zheng","doi":"10.1007/s12598-024-02826-2","DOIUrl":"https://doi.org/10.1007/s12598-024-02826-2","url":null,"abstract":"<p>Monochloroacetic acid (MCAA) is identified as a highly carcinogenic disinfection by-product in chlorinated drinking water. In this study, a series of CeO<sub>2</sub>-supported Pd catalysts (Pd/MCeO<sub>2</sub>) were synthesized through one-step calcination of Pd-loaded Ce-UiO-66-BDC (Ce-MOF), and the liquid-phase catalytic hydrodechlorination of MCAA was explored using these catalysts. For comparison, Pd/CeO<sub>2</sub> catalysts were additionally synthesized using the conventional impregnation method. The characterization results reveal that the catalysts exhibit strong metal–support interaction, leading to high Pd dispersion and Pd<sup><i>n</i>+</sup> content. Additionally, the calcination temperature significantly influences catalytic performance, with the catalyst calcined at 500 °C (Pd/MCeO<sub>2</sub>-500) demonstrating the highest catalytic activity and achieving complete dechlorination of MCAA within 50 min. Furthermore, it is found that the catalytic MCAA hydrodechlorination using the catalysts adheres to the Langmuir–Hinshelwood model. Accordingly, low reaction pH is favorable for the catalytic hydrodechlorination of MCAA, enhancing MCAA adsorption on the catalyst surface due to the electrostatic interaction between MCAA and the catalyst surface. Theoretical results suggest that the presence of Pd<sup><i>n</i>+</sup> efficiently facilitates MCAA adsorption and C–Cl cleavage, thus significantly enhancing the liquid-phase catalytic hydrodechlorination.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>\u0000","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":8.8,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515671","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-02DOI: 10.1007/s12598-024-02818-2
Xin-Liang Han, Jie Zhang, Zuo-Shu Wang, Hussein A. Younus, De-Wei Wang
The aqueous ammonium ion (NH4+) is a promising charge carrier in virtue of its safety, environmental friendliness, abundant resources and small hydrated ionic size. The exploration of NH4+ host electrodes with good reversibility and large storage capacity to construct high-performance ammonium-ion hybrid capacitors (AIHCs), however, is still in its infancy. Herein, a facile etching technique is put forward to produce oxygen-deficient MnO2 (Od-MnO2) as the electrode material for NH4+ storage. According to the experimental and theoretical calculation results, the etching process not only creates more porosity, offering abundant active sites, but also generates abundant oxygen vacancies, which modify the structure of pristine MnO2, enhance charge storage capacity and boost ion diffusion kinetics. Consequently, Od-MnO2 can deliver a specific capacity of 155 mAh·g−1 at 0.5 A·g−1 and a good long-term cycling stability with 86.8% capacity maintained after 10,000 cycles at 5.0 A·g−1. Additionally, the NH4+ storage mechanism was evidenced by several ex-situ characterization analyses. To examine the actual implementation of Od-MnO2 as a positive electrode for NH4+ full device, AIHCs are assembled with activated carbon functionalized with Fe3O4 nanoparticles (Fe3O4@AC) as a negative electrode. A high specific capacitance of 184 F·g−1 at 0.5 A·g−1, satisfactory energy density of 102 Wh·kg−1 at 500 W·kg−1, a low self-discharge rate and good cycling durability after 10,000 cycles are attained. The electrochemical performance of these AIHCs is comparable to or surpass those of traditional supercapacitors with metal ions as charge carriers, highlighting the advantages of structural modification in enhancing the NH4+ storage performance.
{"title":"Engineering the microstructures of manganese dioxide coupled with oxygen vacancies for boosting aqueous ammonium-ion storage in hybrid capacitors","authors":"Xin-Liang Han, Jie Zhang, Zuo-Shu Wang, Hussein A. Younus, De-Wei Wang","doi":"10.1007/s12598-024-02818-2","DOIUrl":"https://doi.org/10.1007/s12598-024-02818-2","url":null,"abstract":"<p>The aqueous ammonium ion (NH<sub>4</sub><sup>+</sup>) is a promising charge carrier in virtue of its safety, environmental friendliness, abundant resources and small hydrated ionic size. The exploration of NH<sub>4</sub><sup>+</sup> host electrodes with good reversibility and large storage capacity to construct high-performance ammonium-ion hybrid capacitors (AIHCs), however, is still in its infancy. Herein, a facile etching technique is put forward to produce oxygen-deficient MnO<sub>2</sub> (O<sub>d</sub>-MnO<sub>2</sub>) as the electrode material for NH<sub>4</sub><sup>+</sup> storage. According to the experimental and theoretical calculation results, the etching process not only creates more porosity, offering abundant active sites, but also generates abundant oxygen vacancies, which modify the structure of pristine MnO<sub>2</sub>, enhance charge storage capacity and boost ion diffusion kinetics. Consequently, O<sub>d</sub>-MnO<sub>2</sub> can deliver a specific capacity of 155 mAh·g<sup>−1</sup> at 0.5 A·g<sup>−1</sup> and a good long-term cycling stability with 86.8% capacity maintained after 10,000 cycles at 5.0 A·g<sup>−1</sup>. Additionally, the NH<sub>4</sub><sup>+</sup> storage mechanism was evidenced by several ex-situ characterization analyses. To examine the actual implementation of O<sub>d</sub>-MnO<sub>2</sub> as a positive electrode for NH<sub>4</sub><sup>+</sup> full device, AIHCs are assembled with activated carbon functionalized with Fe<sub>3</sub>O<sub>4</sub> nanoparticles (Fe<sub>3</sub>O<sub>4</sub>@AC) as a negative electrode. A high specific capacitance of 184 F·g<sup>−1</sup> at 0.5 A·g<sup>−1</sup>, satisfactory energy density of 102 Wh·kg<sup>−1</sup> at 500 W·kg<sup>−1</sup>, a low self-discharge rate and good cycling durability after 10,000 cycles are attained. The electrochemical performance of these AIHCs is comparable to or surpass those of traditional supercapacitors with metal ions as charge carriers, highlighting the advantages of structural modification in enhancing the NH<sub>4</sub><sup>+</sup> storage performance.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>\u0000","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":8.8,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-02DOI: 10.1007/s12598-024-02813-7
Mei-Qian Fu, Yu-Yang Han, Yan-Mei Nie, Yan-Di Liu, Yue Liu, Peng He, Wei-Dong Yu, Xiang Li, Piao He, Juan Li, Jun Yan
Photothermal conversion is one of the key technologies in solar energy collection, seawater desalination, photothermal treatment and other important fields. In order to develop next generation photothermal materials, four polyoxometalates, [(CH3)2NH2]12H5[Ni3Mo18O54(HPO3)10(PO4)]·18H2O (Compound 1), [(CH3)2NH2]1Na11[Ni2Mo8O22(HPO3)10]·16H2O (Compound 2), Na15(OH)5[Mo6O18(HPO3)4]2[MoO]1.5·16H2O (Compound 3), [(CH3)2NH2]4Na11[Na[Mo6O15(HPO3)4]2]·18H2O (Compound 4), are successfully designed and synthesized via a microwave-assisted reaction protocol. Compounds 1–4 not only exhibit broad absorption and notable photothermal conversion effects in near-infrared (NIR) region, but also have high photothermal conversion efficiencies and high quality NIR photothermal imaging effects under NIR laser irradiation. Compound 1 shows the best photothermal conversion effect, and it provides a unique model to explore the relationship between the complex metal oxide structure and photothermal conversion behavior at the molecular level. Both the experimental results and theoretical calculations consistently conclude that the charge and degree of electron delocalization on the Cluster have a robust influence on the photothermal conversion, as well as the aggregation microstructures.
{"title":"Photothermal conversion property studies of polyoxophosphitemolybdate derivatives through microwave-assisted synthesis","authors":"Mei-Qian Fu, Yu-Yang Han, Yan-Mei Nie, Yan-Di Liu, Yue Liu, Peng He, Wei-Dong Yu, Xiang Li, Piao He, Juan Li, Jun Yan","doi":"10.1007/s12598-024-02813-7","DOIUrl":"https://doi.org/10.1007/s12598-024-02813-7","url":null,"abstract":"<p>Photothermal conversion is one of the key technologies in solar energy collection, seawater desalination, photothermal treatment and other important fields. In order to develop next generation photothermal materials, four polyoxometalates, [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>]<sub>12</sub>H<sub>5</sub>[Ni<sub>3</sub>Mo<sub>18</sub>O<sub>54</sub>(HPO<sub>3</sub>)<sub>10</sub>(PO<sub>4</sub>)]·18H<sub>2</sub>O (Compound 1), [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>]<sub>1</sub>Na<sub>11</sub>[Ni<sub>2</sub>Mo<sub>8</sub>O<sub>22</sub>(HPO<sub>3</sub>)<sub>10</sub>]·16H<sub>2</sub>O (Compound 2), Na<sub>15</sub>(OH)<sub>5</sub>[Mo<sub>6</sub>O<sub>18</sub>(HPO<sub>3</sub>)<sub>4</sub>]<sub>2</sub>[MoO]<sub>1.5</sub>·16H<sub>2</sub>O (Compound 3), [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>]<sub>4</sub>Na<sub>11</sub>[Na[Mo<sub>6</sub>O<sub>15</sub>(HPO<sub>3</sub>)<sub>4</sub>]<sub>2</sub>]·18H<sub>2</sub>O (Compound 4), are successfully designed and synthesized via a microwave-assisted reaction protocol. Compounds 1–4 not only exhibit broad absorption and notable photothermal conversion effects in near-infrared (NIR) region, but also have high photothermal conversion efficiencies and high quality NIR photothermal imaging effects under NIR laser irradiation. Compound 1 shows the best photothermal conversion effect, and it provides a unique model to explore the relationship between the complex metal oxide structure and photothermal conversion behavior at the molecular level. Both the experimental results and theoretical calculations consistently conclude that the charge and degree of electron delocalization on the Cluster have a robust influence on the photothermal conversion, as well as the aggregation microstructures.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>\u0000","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":8.8,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515664","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
With the swift advancement of renewable energy and escalating demands for energy storage, potassium-ion batteries (PIBs) are increasingly recognized as a potent energy storage technology. Various carbon anode materials have been utilized for PIBs anodes owing to their superior K+ storage capacity, outstanding cycling performance, elevated capacity, and cost-effectiveness. Therefore, it is imperative to explore and improve carbon anode materials. This review meticulously encapsulates the recent scholarly advancements in carbon anode materials for PIBs. It elucidates the operational mechanisms of carbon anode for PIBs, provides a synopsis of diverse carbon materials, and deliberates on the prevalent challenges, including cycling stability and potassium-ion diffusion rates. Although soft and hard carbon augmented potassium-ion capacities, the expansive surface areas coupled with the large ionic radius of K+ pose substantial challenges to their structural design and optimization. Consequently, this review outlines strategic approaches to the design of carbon materials for excellent potassium storage performance, including the expansion of interlayer spacing, modification of morphology, heteroatom doping, structural defect regulation, incorporation of porous structures, and development of carbon–carbon composites. Finally, the challenges and prospective solutions of carbon anode materials for PIBs with superior energy density and cycling stability were proposed, providing a reasonable guidance for regulation design of carbon materials.
{"title":"Design and optimization of carbon materials as anodes for advanced potassium-ion storage","authors":"Xiang Liu, Jian-Hua Chu, Zi-Xian Wang, Shao-Wei Hu, Zi-Yi Cheng, Ke-Ning Liu, Chao-Jie Zhang, Li-Qiang Zhang, Li-Dong Xing, Wei Wang","doi":"10.1007/s12598-024-02843-1","DOIUrl":"https://doi.org/10.1007/s12598-024-02843-1","url":null,"abstract":"<p>With the swift advancement of renewable energy and escalating demands for energy storage, potassium-ion batteries (PIBs) are increasingly recognized as a potent energy storage technology. Various carbon anode materials have been utilized for PIBs anodes owing to their superior K<sup>+</sup> storage capacity, outstanding cycling performance, elevated capacity, and cost-effectiveness. Therefore, it is imperative to explore and improve carbon anode materials. This review meticulously encapsulates the recent scholarly advancements in carbon anode materials for PIBs. It elucidates the operational mechanisms of carbon anode for PIBs, provides a synopsis of diverse carbon materials, and deliberates on the prevalent challenges, including cycling stability and potassium-ion diffusion rates. Although soft and hard carbon augmented potassium-ion capacities, the expansive surface areas coupled with the large ionic radius of K<sup>+</sup> pose substantial challenges to their structural design and optimization. Consequently, this review outlines strategic approaches to the design of carbon materials for excellent potassium storage performance, including the expansion of interlayer spacing, modification of morphology, heteroatom doping, structural defect regulation, incorporation of porous structures, and development of carbon–carbon composites. Finally, the challenges and prospective solutions of carbon anode materials for PIBs with superior energy density and cycling stability were proposed, providing a reasonable guidance for regulation design of carbon materials.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":8.8,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515667","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-02DOI: 10.1007/s12598-024-02836-0
Ze-Xiang Yin, Yu-Dan Li, Yu-Huan Ye, Yuan Liu, Mian-Feng Li, Zi-Jun Yang, Xue-Rong Zheng, Hao-Zhi Wang, Yang Wang, Yi-Da Deng
Single-atom catalysts (SACs) have been widely utilized in electrochemical nitrogen reduction reactions (NRR) due to their high atomic utilization and selectivity. Owing to the unique sp/sp2 co-hybridization, graphyne materials can offer stable adsorption sites for single metal atoms. To investigate the influence of the sp/sp2 hybrid carbon ratio on the electrocatalytic NRR performance of graphyne, a high-throughput screening of 81 catalysts, with 27 transition metals loaded on graphyne (GY1), graphdiyne (GY2), and graphtriyne (GY3), was conducted using first-principles calculations. The results of the screening revealed that Ti@GY3 exhibits the lowest energy barrier for the rate-determining step (0.32 eV) in NRR. Further, to explore the impact of different sp/sp2-hybridized carbon ratios on the catalytic activity of SACs, the mechanism of nitrogen (N2) adsorption, activation, and the comprehensive pathway of NRR on Ti@GY1, Ti@GY2, and Ti@GY3 was systematically investigated. It was found that the ratio of sp/sp2-hybridized carbon can significantly modulate the d-band center of the metal, thus affecting the energy barrier of the rate-determining step in NRR, decreasing from Ti@GY1 (0.59 eV) to Ti@GY2 (0.49 eV), and further to Ti@GY3 (0.32 eV). Additionally, the Hall conductance was found to increase with the bias voltage in the range of 0.4–1 V, as calculated by Nanodcal software, demonstrating an improvement in the conductivity of the SAC. In summary, this work provides theoretical guidance for modulating the electrocatalytic nitrogen reduction activity of SACs by varying the ratio of sp/sp2 hybrid carbon, with Ti@GY3 showing potential as an excellent NRR catalyst.
{"title":"Sp/sp2 carbon ratio-driven high-throughput screening of electrocatalytic nitrogen reduction performance on transition metal single-atom catalysts","authors":"Ze-Xiang Yin, Yu-Dan Li, Yu-Huan Ye, Yuan Liu, Mian-Feng Li, Zi-Jun Yang, Xue-Rong Zheng, Hao-Zhi Wang, Yang Wang, Yi-Da Deng","doi":"10.1007/s12598-024-02836-0","DOIUrl":"https://doi.org/10.1007/s12598-024-02836-0","url":null,"abstract":"<p>Single-atom catalysts (SACs) have been widely utilized in electrochemical nitrogen reduction reactions (NRR) due to their high atomic utilization and selectivity. Owing to the unique sp/sp<sup>2</sup> co-hybridization, graphyne materials can offer stable adsorption sites for single metal atoms. To investigate the influence of the sp/sp<sup>2</sup> hybrid carbon ratio on the electrocatalytic NRR performance of graphyne, a high-throughput screening of 81 catalysts, with 27 transition metals loaded on graphyne (GY1), graphdiyne (GY2), and graphtriyne (GY3), was conducted using first-principles calculations. The results of the screening revealed that Ti@GY3 exhibits the lowest energy barrier for the rate-determining step (0.32 eV) in NRR. Further, to explore the impact of different sp/sp<sup>2</sup>-hybridized carbon ratios on the catalytic activity of SACs, the mechanism of nitrogen (N<sub>2</sub>) adsorption, activation, and the comprehensive pathway of NRR on Ti@GY1, Ti@GY2, and Ti@GY3 was systematically investigated. It was found that the ratio of sp/sp<sup>2</sup>-hybridized carbon can significantly modulate the <i>d</i>-band center of the metal, thus affecting the energy barrier of the rate-determining step in NRR, decreasing from Ti@GY1 (0.59 eV) to Ti@GY2 (0.49 eV), and further to Ti@GY3 (0.32 eV). Additionally, the Hall conductance was found to increase with the bias voltage in the range of 0.4–1 V, as calculated by Nanodcal software, demonstrating an improvement in the conductivity of the SAC. In summary, this work provides theoretical guidance for modulating the electrocatalytic nitrogen reduction activity of SACs by varying the ratio of sp/sp<sup>2</sup> hybrid carbon, with Ti@GY3 showing potential as an excellent NRR catalyst.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>\u0000","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":8.8,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The high-value utilization of manganese ore tailings is of great significance for saving mineral resources and achieving environmental protection. Herein, an olivine LiFe0.5Mn0.5PO4/rGO composite is synthesized by a simple precipitation method and subsequent high-temperature calcination process using the manganese ore tailings as raw material. The prepared LiFe0.5Mn0.5PO4/rGO composite exhibits superior cycling stability (with 113.5 mAh·g−1 after 300 cycles at 1.0C (1.0C = 170 mA·g−1)) and superior rate performance (with 65.6 mAh·g−1 at 10.0C). Ex-situ XRD and electrochemical impedance spectroscopy (EIS) analyses evidence that the LiFe0.5Mn0.5PO4/rGO material has excellent structural stability and electrochemical reversibility during charge and discharge processes. Furthermore, the LiFe0.5Mn0.5PO4/rGO//graphite full Li-ion battery also exhibits excellent cycling stability indicating its potential commercialization value.
{"title":"An olivine LiFe0.5Mn0.5PO4/rGO composite cathode material prepared from manganese ore tailings with excellent lithium storage performance","authors":"Wen-Han Xu, Jin-Huan Yao, Qi-Ze Huang, Shao-Shuai Bai, Yan-Wei Li, Ji-Qiong Jiang, Jian-Wen Yang","doi":"10.1007/s12598-024-02755-0","DOIUrl":"https://doi.org/10.1007/s12598-024-02755-0","url":null,"abstract":"<p>The high-value utilization of manganese ore tailings is of great significance for saving mineral resources and achieving environmental protection. Herein, an olivine LiFe<sub>0.5</sub>Mn<sub>0.5</sub>PO<sub>4</sub>/rGO composite is synthesized by a simple precipitation method and subsequent high-temperature calcination process using the manganese ore tailings as raw material. The prepared LiFe<sub>0.5</sub>Mn<sub>0.5</sub>PO<sub>4</sub>/rGO composite exhibits superior cycling stability (with 113.5 mAh·g<sup>−1</sup> after 300 cycles at 1.0C (1.0C = 170 mA·g<sup>−1</sup>)) and superior rate performance (with 65.6 mAh·g<sup>−1</sup> at 10.0C). Ex-situ XRD and electrochemical impedance spectroscopy (EIS) analyses evidence that the LiFe<sub>0.5</sub>Mn<sub>0.5</sub>PO<sub>4</sub>/rGO material has excellent structural stability and electrochemical reversibility during charge and discharge processes. Furthermore, the LiFe<sub>0.5</sub>Mn<sub>0.5</sub>PO<sub>4</sub>/rGO//graphite full Li-ion battery also exhibits excellent cycling stability indicating its potential commercialization value.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>\u0000","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":8.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515663","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-01DOI: 10.1007/s12598-024-02679-9
Ming-Hui Li, Jing Li, Xiao-Yu Zheng, Yao Zhou
Single-atom catalysts have risen significant attention in the realm of green electrocatalytic energy conversion to address energy and environmental sustainability challenges. Transition metal dichalcogenide (TMD)-based single-atom catalysts are considered highly effective in electrocatalysis due to the TMDs' notable specific surface area, tunable elemental species and efficient utilization of single atoms. In order to enhance electrocatalytic performance, it is imperative to elaborately engineer the local environment surrounding the active sites of single atoms within TMDs. In this review, we initially explore the effects of synthesis methods on single-atom active sites and the influence of loading of single atoms on catalytic performance for TMDs. The modulation strategies of the local environment surrounding single-atom sites in TMDs are elaborated, including substitution engineering, surface adsorption, vacancies, spatial confinement and dual-atom site strategies. For each modulation strategy, the effects of diverse local environments on various electrocatalytic applications are presented, such as the oxygen evolution reaction, oxygen reduction reaction, nitrogen reduction reaction, CO2 reduction reaction and CO oxidation. Ultimately, this study presents a comprehensive overview of the challenges encountered and the potential directions for the advancement of single-atom catalysts based on TMDs in the realm of electrocatalysis.
{"title":"Local environment regulation of transition metal dichalcogenide-based single-atom catalysts","authors":"Ming-Hui Li, Jing Li, Xiao-Yu Zheng, Yao Zhou","doi":"10.1007/s12598-024-02679-9","DOIUrl":"https://doi.org/10.1007/s12598-024-02679-9","url":null,"abstract":"<p>Single-atom catalysts have risen significant attention in the realm of green electrocatalytic energy conversion to address energy and environmental sustainability challenges. Transition metal dichalcogenide (TMD)-based single-atom catalysts are considered highly effective in electrocatalysis due to the TMDs' notable specific surface area, tunable elemental species and efficient utilization of single atoms. In order to enhance electrocatalytic performance, it is imperative to elaborately engineer the local environment surrounding the active sites of single atoms within TMDs. In this review, we initially explore the effects of synthesis methods on single-atom active sites and the influence of loading of single atoms on catalytic performance for TMDs. The modulation strategies of the local environment surrounding single-atom sites in TMDs are elaborated, including substitution engineering, surface adsorption, vacancies, spatial confinement and dual-atom site strategies. For each modulation strategy, the effects of diverse local environments on various electrocatalytic applications are presented, such as the oxygen evolution reaction, oxygen reduction reaction, nitrogen reduction reaction, CO<sub>2</sub> reduction reaction and CO oxidation. Ultimately, this study presents a comprehensive overview of the challenges encountered and the potential directions for the advancement of single-atom catalysts based on TMDs in the realm of electrocatalysis.</p><h3 data-test=\"abstract-sub-heading\">Graphical Abstract</h3>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":8.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141508587","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-28DOI: 10.1007/s12598-024-02850-2
Xue-Qin Zhang, Ru-Yue Su, Xiong Gao, Jing-Yi Chen, Guo Liu, Ru-Jie He, Ying Li
Benefiting from excellent mechanical properties and low density, cellular ceramic structures (CCSs) are competitive candidates as structural components. However, inherent brittleness from strong chemical bonds among atoms extremely impeded CCSs’ application. Natural materials occupied outstanding strength and toughness simultaneously due to the dual-phase interpenetrated structure. Inspired by natural materials, it was proposed to fabricate coating covered and fulfilled polyurea/CCS interpenetrated composites (C/CCSs and B/CCSs) to circumvent the brittleness of 3D-printed Al2O3 CCSs. It was demonstrated that polyurea coating had less effect on the compressive strength of C/CCSs but tremendously improved their energy-absorbing ability. The energy-absorbing ability of C/CCSs was improved from 26.48–52.57 kJ·m−3 of CCSs to 1.04–1.89 MJ·m−3 because of the extended plateau stage. Furthermore, compressive strength and energy-absorbing ability of B/CCSs were strengthened to 1.33–1.36 and 2.84–4.61 times of C/CCSs, respectively. Besides, failure mode of C/CCSs changed from localized deformation to fracturing entirely with the increase in relative density of CCSs inside, which was the same as that of CCSs. However, with the help of polyurea coating, C/CCSs were still intact at strains up to 60%, which would never fail catastrophically as CCSs at low strains. B/CCSs tended to fracture as a whole, which was not influenced by relative density of pristine CCSs. It was believed that this work provided a creative way to circumvent the brittleness of CCSs and improve their mechanical performances.
{"title":"Circumventing brittleness of 3D-printed Al2O3 cellular ceramic structures via compositing with polyurea","authors":"Xue-Qin Zhang, Ru-Yue Su, Xiong Gao, Jing-Yi Chen, Guo Liu, Ru-Jie He, Ying Li","doi":"10.1007/s12598-024-02850-2","DOIUrl":"https://doi.org/10.1007/s12598-024-02850-2","url":null,"abstract":"<p>Benefiting from excellent mechanical properties and low density, cellular ceramic structures (CCSs) are competitive candidates as structural components. However, inherent brittleness from strong chemical bonds among atoms extremely impeded CCSs’ application. Natural materials occupied outstanding strength and toughness simultaneously due to the dual-phase interpenetrated structure. Inspired by natural materials, it was proposed to fabricate coating covered and fulfilled polyurea/CCS interpenetrated composites (C/CCSs and B/CCSs) to circumvent the brittleness of 3D-printed Al<sub>2</sub>O<sub>3</sub> CCSs. It was demonstrated that polyurea coating had less effect on the compressive strength of C/CCSs but tremendously improved their energy-absorbing ability. The energy-absorbing ability of C/CCSs was improved from 26.48–52.57 kJ·m<sup>−3</sup> of CCSs to 1.04–1.89 MJ·m<sup>−3</sup> because of the extended plateau stage. Furthermore, compressive strength and energy-absorbing ability of B/CCSs were strengthened to 1.33–1.36 and 2.84–4.61 times of C/CCSs, respectively. Besides, failure mode of C/CCSs changed from localized deformation to fracturing entirely with the increase in relative density of CCSs inside, which was the same as that of CCSs. However, with the help of polyurea coating, C/CCSs were still intact at strains up to 60%, which would never fail catastrophically as CCSs at low strains. B/CCSs tended to fracture as a whole, which was not influenced by relative density of pristine CCSs. It was believed that this work provided a creative way to circumvent the brittleness of CCSs and improve their mechanical performances.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>\u0000","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":8.8,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515670","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-28DOI: 10.1007/s12598-024-02815-5
Lei-Chao Meng, Hao Zhang, Le Kang, Yi Zhang, Neng-Fei Yu, Fan Zhang, Hui-Ling Du
Designing bifunctional oxygen reduction/evolution (ORR/OER) catalysts with high activity, robust stability and low cost is the key to accelerating the commercialization of rechargeable zinc-air battery (RZAB). Here, we propose a template-assisted electrospinning strategy to in situ fabricate 3D fibers consisting of FeNi nanoparticles embedded into N-doped hollow porous carbon nanospheres (FeNi@NHCFs) as the stable binder-free integrated air cathode in RZAB. 3D interconnected conductive fiber networks provide fast electron transfer pathways and strengthen the mechanical flexibility. Meanwhile, N-doped hollow porous carbon nanospheres not only evenly confine FeNi nanoparticles to provide sufficient catalytic active sites, but also endow optimum mass transfer environment to reduce diffusion barrier. The RZABs assembled by FeNi@NHCFs as integrated air cathodes exhibit outstanding battery performance with high open-circuit voltage, large discharge specific capacity and power density, durable cyclic stability and great flexibility. Thus, this work brings a useful strategy to fabricate the integrated electrodes without using any polymeric binders for metal air batteries and other related fields.
Graphical abstract
设计具有高活性、高稳定性和低成本的双功能氧还原/进化（ORR/OER）催化剂是加速可充电锌空气电池（RZAB）商业化的关键。在此，我们提出了一种模板辅助电纺丝策略，以原位制造由嵌入 N 掺杂中空多孔碳纳米球（FeNi@NHCFs）的 FeNi 纳米颗粒组成的三维纤维，作为 RZAB 中稳定的无粘结剂集成空气阴极。三维相互连接的导电纤维网络提供了快速的电子传输途径，并增强了机械灵活性。同时，掺杂 N 的中空多孔碳纳米球不仅能均匀地约束镍铁纳米颗粒，提供足够的催化活性位点，还能提供最佳的传质环境，降低扩散阻力。由 FeNi@NHCFs 组装成的 RZABs 作为集成空气阴极，具有开路电压高、放电比容量和功率密度大、持久循环稳定性和灵活性强等优异的电池性能。因此，这项工作为金属空气电池及其他相关领域提供了一种不使用任何聚合物粘合剂制造集成电极的有用策略。
{"title":"Robust and flexible 3D integrated FeNi@NHCFs air electrode for high-performance rechargeable zinc-air battery","authors":"Lei-Chao Meng, Hao Zhang, Le Kang, Yi Zhang, Neng-Fei Yu, Fan Zhang, Hui-Ling Du","doi":"10.1007/s12598-024-02815-5","DOIUrl":"https://doi.org/10.1007/s12598-024-02815-5","url":null,"abstract":"<p>Designing bifunctional oxygen reduction/evolution (ORR/OER) catalysts with high activity, robust stability and low cost is the key to accelerating the commercialization of rechargeable zinc-air battery (RZAB). Here, we propose a template-assisted electrospinning strategy to in situ fabricate 3D fibers consisting of FeNi nanoparticles embedded into N-doped hollow porous carbon nanospheres (FeNi@NHCFs) as the stable binder-free integrated air cathode in RZAB. 3D interconnected conductive fiber networks provide fast electron transfer pathways and strengthen the mechanical flexibility. Meanwhile, N-doped hollow porous carbon nanospheres not only evenly confine FeNi nanoparticles to provide sufficient catalytic active sites, but also endow optimum mass transfer environment to reduce diffusion barrier. The RZABs assembled by FeNi@NHCFs as integrated air cathodes exhibit outstanding battery performance with high open-circuit voltage, large discharge specific capacity and power density, durable cyclic stability and great flexibility. Thus, this work brings a useful strategy to fabricate the integrated electrodes without using any polymeric binders for metal air batteries and other related fields.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":8.8,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141508588","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-26DOI: 10.1007/s12598-024-02759-w
Xue-Yu Man, Ze-Wen Sun, Shan-He Li, Gang Xu, Wen-Juan Li, Zhen-Lei Zhang, Hong Liang, Feng Yang
Cisplatin resistance is the main cause for the failure of cancer therapy. To solve the problem, we proposed to develop a novel human serum albumin (HSA) nanoplatform to integrate chemotherapy, photothermal therapy (PTT) and immunotherapy. To this end, we obtained a platinum compound (C5) with significant cytotoxicity in the cisplatin-resistant SKOV-3 cells (SKOV-3/DDP), and then innovatively constructed photosensitizer (indocyanine green (ICG))-encapsulated HSA-C5 complex nanoparticles (ICG@HSA-C5 NPs). The ICG@HSA-C5 NPs exhibited excellent photothermal performances in vitro and in vivo. Importantly, the in vivo results revealed that HSA enhanced the antitumor effect of C5 and that the combination of chemotherapy and PTT could significantly inhibit cisplatin-resistant tumor growth and improved the targeting abilities of C5 and ICG, and reduced their side effects. We also confirmed that ICG@HSA-C5 NPs killed the SKOV-3/DDP cells via gasdermin E (GSDME)-mediated pyroptosis and pyroptosis-induced immune responses, thereby synergistically leading to the death of the SKOV-3/DDP cells.
{"title":"Development of a Pt(II) compound based on indocyanine green@human serum albumin nanoparticles: integrating phototherapy, chemotherapy and immunotherapy to overcome tumor cisplatin resistance","authors":"Xue-Yu Man, Ze-Wen Sun, Shan-He Li, Gang Xu, Wen-Juan Li, Zhen-Lei Zhang, Hong Liang, Feng Yang","doi":"10.1007/s12598-024-02759-w","DOIUrl":"https://doi.org/10.1007/s12598-024-02759-w","url":null,"abstract":"<p>Cisplatin resistance is the main cause for the failure of cancer therapy. To solve the problem, we proposed to develop a novel human serum albumin (HSA) nanoplatform to integrate chemotherapy, photothermal therapy (PTT) and immunotherapy. To this end, we obtained a platinum compound (C5) with significant cytotoxicity in the cisplatin-resistant SKOV-3 cells (SKOV-3/DDP), and then innovatively constructed photosensitizer (indocyanine green (ICG))-encapsulated HSA-C5 complex nanoparticles (ICG@HSA-C5 NPs). The ICG@HSA-C5 NPs exhibited excellent photothermal performances in vitro and in vivo. Importantly, the in vivo results revealed that HSA enhanced the antitumor effect of C5 and that the combination of chemotherapy and PTT could significantly inhibit cisplatin-resistant tumor growth and improved the targeting abilities of C5 and ICG, and reduced their side effects. We also confirmed that ICG@HSA-C5 NPs killed the SKOV-3/DDP cells via gasdermin E (GSDME)-mediated pyroptosis and pyroptosis-induced immune responses, thereby synergistically leading to the death of the SKOV-3/DDP cells.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":8.8,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141508589","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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