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}
High-performance bifunctional oxygen electrocatalysts that simultaneously boost the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) need to be developed for advanced rechargeable Zn-air battery applications. In this work, a zeolitic imidazolate framework (ZIF)-phase conversion associated with a subsequent thermal fixing strategy was developed to fabricate bimetallic CoFe single atoms/clusters embedded in N-doped carbon (denoted as CoFe–N–C) nanorods, which can serve as efficient bifunctional ORR/OER electrocatalysts. Microstructural observation and X-ray absorption spectroscopy analysis confirm the co-existence of highly active Co/Fe–Nx dual sites and CoFe alloy nanoclusters. X-ray photoelectron spectroscopy (XPS) results prove that implanting secondary Fe atoms into Co–N–C matrix nanorods can induce electronic redistribution of atomic Co/Fe active sites and generate synergistic effects, which would optimize the adsorption energy of the reaction intermediates and thus enhance the bifunctional ORR/OER activity. The bimetallic CoFe–N–C nanorods exhibit significantly enhanced bifunctional ORR/OER activity and stability than the monometallic Co/Fe–N–C nanorods in alkaline electrolytes in terms of a very positive half-wave potential of 0.90 V (vs. reversible hydrogen electrode (RHE)) for ORR, and an overpotential of 440 mV to reach current density of 10 mA·cm−2 for OER, yielding a small overpotential gap of 0.77 V. Furthermore, the rechargeable Zn-air batteries using bimetallic CoFe–N–C nanorods as air–cathode catalyst demonstrates peak power density of 200.7 mW·cm−2 and robust cycling stability of up to 200 h, corresponding to 1200 discharge–charge cycles.
{"title":"ZIF-derived N-doped carbon nanorods supporting bimetallic CoFe single-atoms/nanoclusters as bifunctional oxygen electrocatalysts for stable Zn-air batteries","authors":"Hong-Shuang Fan, Fei-Xiang Ma, Zi-Hao Liu, Wen-Hui Wang, Zheng-Qi Liu, Xiong-Yi Liang, Yue Du, Yang-Yang Li, Liang Zhen, Cheng-Yan Xu","doi":"10.1007/s12598-024-02676-y","DOIUrl":"https://doi.org/10.1007/s12598-024-02676-y","url":null,"abstract":"<p>High-performance bifunctional oxygen electrocatalysts that simultaneously boost the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) need to be developed for advanced rechargeable Zn-air battery applications. In this work, a zeolitic imidazolate framework (ZIF)-phase conversion associated with a subsequent thermal fixing strategy was developed to fabricate bimetallic CoFe single atoms/clusters embedded in N-doped carbon (denoted as CoFe–N–C) nanorods, which can serve as efficient bifunctional ORR/OER electrocatalysts. Microstructural observation and X-ray absorption spectroscopy analysis confirm the co-existence of highly active Co/Fe–N<sub><i>x</i></sub> dual sites and CoFe alloy nanoclusters. X-ray photoelectron spectroscopy (XPS) results prove that implanting secondary Fe atoms into Co–N–C matrix nanorods can induce electronic redistribution of atomic Co/Fe active sites and generate synergistic effects, which would optimize the adsorption energy of the reaction intermediates and thus enhance the bifunctional ORR/OER activity. The bimetallic CoFe–N–C nanorods exhibit significantly enhanced bifunctional ORR/OER activity and stability than the monometallic Co/Fe–N–C nanorods in alkaline electrolytes in terms of a very positive half-wave potential of 0.90 V (vs. reversible hydrogen electrode (RHE)) for ORR, and an overpotential of 440 mV to reach current density of 10 mA·cm<sup>−2</sup> for OER, yielding a small overpotential gap of 0.77 V. Furthermore, the rechargeable Zn-air batteries using bimetallic CoFe–N–C nanorods as air–cathode catalyst demonstrates peak power density of 200.7 mW·cm<sup>−2</sup> and robust cycling stability of up to 200 h, corresponding to 1200 discharge–charge cycles.</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":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515736","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 : 2024-06-25DOI: 10.1007/s12598-024-02854-y
Ming-Cai Pan, Jun-Qiang Xu, Yong Peng, Ning-Ning Liang, Si Lan, Qi Zhou, Ke-Hong Wang
Heat treatment significantly influences homogeneous material microstructures and mechanical properties, which can be improved by an optimal heat treatment process. However, heat treatment application to heterogeneous materials presents significant challenges due to compositional and microstructural heterogeneities. Herein, a laminated heterostructured alloy comprising alternating 316L stainless steel (SS) and 18Ni300 maraging steel (MS) layers fabricated using wire and arc additive manufacturing was investigated. A solution treatment was applied at 900 °C for 0.5 h. Subsequently, the solution-treated and as-fabricated (AF) samples were aged at 500 °C for 4 h; these samples were denoted SA and AT, respectively. The AT phase compositions and orientations were similar to those of AF. The SA 316L SS layer resembled that of AF, but the SA 18Ni300 MS layers exhibited a reduced austenite phase fraction and refined grain size, attributable to solid-state transformation. In the AT sample, aging induced the formation of nanoscale acicular ω phase and ellipsoidal Ni3Ti, Fe2Mo, and X precipitates in the 18Ni300 MS layers. Conversely, the SA precipitates contained acicular FeNi2 and ellipsoidal ω, Ni3Ti, and X precipitates, and their fractions were lower than those in AT precipitates. The 18Ni300 MS layer microhardness in the heat-treated samples increased due to nanoprecipitation, but the 316L SS layer microhardness resembled that of AF. The AT and SA ultimate tensile strengths increased to (1360 ± 50) and (1473 ± 41) MPa, respectively, attributable to precipitation strengthening. The SA 316L SS layer exhibited a high stress-induced martensite fraction, enhancing the ductility of heated samples.
Graphical abstract
热处理对均质材料的微观结构和机械性能有很大影响，而最佳的热处理工艺可以改善这些性能。然而，由于成分和微观结构的异质性，对异质材料进行热处理面临着巨大挑战。本文研究了一种层状异质结构合金，该合金由交替的 316L 不锈钢（SS）层和 18Ni300 马氏体时效钢（MS）层组成，使用线材和电弧增材制造技术制造。在 900 °C 下进行了 0.5 小时的固溶处理。随后，在 500 °C 下对固溶处理过的样品和原样（AF）进行了 4 小时的老化处理；这些样品分别称为 SA 和 AT。AT 相的组成和取向与 AF 相似。SA 316L SS 层与 AF 类似，但 SA 18Ni300 MS 层的奥氏体相分数降低，晶粒尺寸细化，这归因于固态转变。在 AT 样品中，老化诱导在 18Ni300 MS 层中形成纳米级针状 ω 相和椭圆形 Ni3Ti、Fe2Mo 和 X 沉淀。相反，SA沉淀中含有针状的FeNi2和椭圆形的ω、Ni3Ti和X沉淀，它们的比例低于AT沉淀。热处理样品中 18Ni300 MS 层的显微硬度因纳米析出而增加，但 316L SS 层的显微硬度与 AF 类似。由于沉淀强化作用，AT 和 SA 的极限抗拉强度分别增加到（1360 ± 50）和（1473 ± 41）兆帕。SA 316L SS 层表现出较高的应力诱导马氏体分数，增强了加热样品的延展性。
{"title":"Effects of heat treatment on microstructures and properties of a heterostructured alloy with dissimilar components fabricated by WAAM","authors":"Ming-Cai Pan, Jun-Qiang Xu, Yong Peng, Ning-Ning Liang, Si Lan, Qi Zhou, Ke-Hong Wang","doi":"10.1007/s12598-024-02854-y","DOIUrl":"https://doi.org/10.1007/s12598-024-02854-y","url":null,"abstract":"<p>Heat treatment significantly influences homogeneous material microstructures and mechanical properties, which can be improved by an optimal heat treatment process. However, heat treatment application to heterogeneous materials presents significant challenges due to compositional and microstructural heterogeneities. Herein, a laminated heterostructured alloy comprising alternating 316L stainless steel (SS) and 18Ni300 maraging steel (MS) layers fabricated using wire and arc additive manufacturing was investigated. A solution treatment was applied at 900 °C for 0.5 h. Subsequently, the solution-treated and as-fabricated (AF) samples were aged at 500 °C for 4 h; these samples were denoted SA and AT, respectively. The AT phase compositions and orientations were similar to those of AF. The SA 316L SS layer resembled that of AF, but the SA 18Ni300 MS layers exhibited a reduced austenite phase fraction and refined grain size, attributable to solid-state transformation. In the AT sample, aging induced the formation of nanoscale acicular ω phase and ellipsoidal Ni<sub>3</sub>Ti, Fe<sub>2</sub>Mo, and X precipitates in the 18Ni300 MS layers. Conversely, the SA precipitates contained acicular FeNi<sub>2</sub> and ellipsoidal ω, Ni<sub>3</sub>Ti, and X precipitates, and their fractions were lower than those in AT precipitates. The 18Ni300 MS layer microhardness in the heat-treated samples increased due to nanoprecipitation, but the 316L SS layer microhardness resembled that of AF. The AT and SA ultimate tensile strengths increased to (1360 ± 50) and (1473 ± 41) MPa, respectively, attributable to precipitation strengthening. The SA 316L SS layer exhibited a high stress-induced martensite fraction, enhancing the ductility of heated samples.</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":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141508590","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}
Two-dimensional materials are widely considered to be highly promising for the development of photodetectors. To improve the performance of these devices, researchers often employ techniques such as defect engineering. Herein, pressure is employed as a clean and novel means to manipulate the structural and physical properties of EuSbTe3, an emerging two-dimensional semiconductor. The experimental results demonstrate that the structural phase transformation of EuSbTe3 occurs under pressure, with an increase in infrared reflectivity, a band gap closure, and a metallization at pressures. Combined with X-ray diffraction (XRD) and Raman characterizations, it is evident that the pressure-driven transition from semiconductor Pmmn phase to metallic Cmcm phase causes the disappearance of the charge density wave. Furthermore, at a mild pressure, approximately 2 GPa, the maximum photocurrent of EuSbTe3 is three times higher than that at ambient condition, suggesting an untapped potential for various practical applications.
{"title":"Pressure-driven metallization with significant changes of structural and photoelectric properties in two-dimensional EuSbTe3","authors":"Zhi-Kai Zhu, Zhong-Yang Li, Zhen Qin, Yi-Ming Wang, Dong Wang, Xiao-Hui Zeng, Fu-Yang Liu, Hong-Liang Dong, Qing-Yang Hu, Ling-Ping Kong, Hao-Zhe Liu, Wen-Ge Yang, Yan-Feng Guo, Shuai Yan, Xuan Fang, Wei He, Gang Liu","doi":"10.1007/s12598-024-02812-8","DOIUrl":"https://doi.org/10.1007/s12598-024-02812-8","url":null,"abstract":"<p>Two-dimensional materials are widely considered to be highly promising for the development of photodetectors. To improve the performance of these devices, researchers often employ techniques such as defect engineering. Herein, pressure is employed as a clean and novel means to manipulate the structural and physical properties of EuSbTe<sub>3</sub>, an emerging two-dimensional semiconductor. The experimental results demonstrate that the structural phase transformation of EuSbTe<sub>3</sub> occurs under pressure, with an increase in infrared reflectivity, a band gap closure, and a metallization at pressures. Combined with X-ray diffraction (XRD) and Raman characterizations, it is evident that the pressure-driven transition from semiconductor <i>Pmmn</i> phase to metallic <i>Cmcm</i> phase causes the disappearance of the charge density wave. Furthermore, at a mild pressure, approximately 2 GPa, the maximum photocurrent of EuSbTe<sub>3</sub> is three times higher than that at ambient condition, suggesting an untapped potential for various practical applications.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":8.8,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515737","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 : 2024-06-24DOI: 10.1007/s12598-024-02770-1
Wen-Xue Chen, Yue Du, Li-Na Zhou, Zhi-Yi Zhong, Zhi-Xian Shi, Yan Mao, Zi-Quan Zhou, Hao-Yue Feng, Yu Su, Hai-Yan Hu, Shi Li, Dong-Bin Xiong, Jian-Qin Zhou, Yi-Si Liu, Yao Xiao
Electrocatalysts play a crucial role in the performance of rechargeable Zn-air batteries (ZABs), but it is still difficult to produce nonprecious materials with excellent bifunctional oxygen reduction reactions (ORR) and oxygen evolution reactions (OER). Herein, conjugated polyaniline-phytic acid polymer (pANI-PA) was directly calcined to fabricate Co2P nanoparticles embedded in N, P-doped carbon network composites (Co2P@pDC-PA) for metal-air cathodes. The resulting pANI-PA derived Co2P-based carbon composite exhibits exceptional bifunctional ORR/OER activities with a half-wave potential of 0.79 V for ORR and 1.62 V of over-potential for OER at 10 mA·cm−2. Owing to the synergistic effect of its unique three-dimensional (3D) structure, N, P-doped carbon framework, and encapsulated Co2P nanoparticles, as-fabricated composite can be used as a highly efficient air cathode in the rechargeable metal-air battery. The assembled rechargeable ZAB demonstrates a high-power density of 190.0 mW·cm−2 and remarkable cycling stability over 1000 h. This study introduced a novel approach that paves the way for the efficient, cost-effective, and scalable production of bifunctional electrocatalysts for rechargeable ZABs.
{"title":"An universal in-situ phosphating strategy to fabricate high-performance Co2P-based bifunctional oxygen electrocatalyst derived from conjugated polyaniline-phytic acid copolymer","authors":"Wen-Xue Chen, Yue Du, Li-Na Zhou, Zhi-Yi Zhong, Zhi-Xian Shi, Yan Mao, Zi-Quan Zhou, Hao-Yue Feng, Yu Su, Hai-Yan Hu, Shi Li, Dong-Bin Xiong, Jian-Qin Zhou, Yi-Si Liu, Yao Xiao","doi":"10.1007/s12598-024-02770-1","DOIUrl":"https://doi.org/10.1007/s12598-024-02770-1","url":null,"abstract":"<p>Electrocatalysts play a crucial role in the performance of rechargeable Zn-air batteries (ZABs), but it is still difficult to produce nonprecious materials with excellent bifunctional oxygen reduction reactions (ORR) and oxygen evolution reactions (OER). Herein, conjugated polyaniline-phytic acid polymer (pANI-PA) was directly calcined to fabricate Co<sub>2</sub>P nanoparticles embedded in N, P-doped carbon network composites (Co<sub>2</sub>P@pDC-PA) for metal-air cathodes. The resulting pANI-PA derived Co<sub>2</sub>P-based carbon composite exhibits exceptional bifunctional ORR/OER activities with a half-wave potential of 0.79 V for ORR and 1.62 V of over-potential for OER at 10 mA·cm<sup>−2</sup>. Owing to the synergistic effect of its unique three-dimensional (3D) structure, N, P-doped carbon framework, and encapsulated Co<sub>2</sub>P nanoparticles, as-fabricated composite can be used as a highly efficient air cathode in the rechargeable metal-air battery. The assembled rechargeable ZAB demonstrates a high-power density of 190.0 mW·cm<sup>−2</sup> and remarkable cycling stability over 1000 h. This study introduced a novel approach that paves the way for the efficient, cost-effective, and scalable production of bifunctional electrocatalysts for rechargeable ZABs.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":8.8,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515738","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 : 2024-06-24DOI: 10.1007/s12598-024-02820-8
Chu Cheng, Xin-Yu Wang, Ting-An Zhang, Zhi-He Dou, Ke-Xing Song, Meng-Xin Wang, Yan-Shuo Feng, Tao Huang, Hai-Tao Liu, Xiao-Heng Li, Kai Li
CuW is widely used in high-voltage electrical switch contacts, rocket nozzle throat linings, electronic packaging materials and other major high-end technologies. CuW is typically fabricated using infiltration and high-temperature sintering methods based on powder metallurgy. As CuW composites fabricated using these methods have the disadvantages of low density and uneven microstructural distribution, the preparation of CuW composites by aluminothermic reduction was proposed. However, some Al2O3 inclusions produced by aluminothermic reduction do not effectively combine with the slag-making agent CaO to form a liquid slag phase and remain in the CuW composite, resulting in a small number of Al2O3 inclusions in the CuW composites. To overcome this problem, a novel methodology for strengthening metal-slag separation through in situ slagging is proposed. In this study, CuW composites were prepared by metallothermic reduction using Al, AlCa and AlMg as reducing agents. The CuW composites and slag samples were systematically analyzed. The results indicate that the Al2O3 particles produced by aluminothermic reduction can be modified in situ into calcium aluminate and MgO·Al2O3 with lower melting points by using AlCa and AlMg alloys as reducing agents, which strengthens the metal-slag separation. Moreover, AlCa and AlMg exhibited refining effects on the tungsten particles of the CuW composite, where the effect of AlMg was greater than that of AlCa. The slag obtained using the AlCa alloy as a reducing agent was mainly composed of CaWO4, CaAl4O7 and Ca4Al6O12WO4, whereas that obtained using the AlMg alloy was mainly composed of CaWO4, MgAl2O4 and Ca4Al6O12WO4.
{"title":"Metal-slag separation strengthening through in situ slagging during CuW composite preparation by metallothermic reduction","authors":"Chu Cheng, Xin-Yu Wang, Ting-An Zhang, Zhi-He Dou, Ke-Xing Song, Meng-Xin Wang, Yan-Shuo Feng, Tao Huang, Hai-Tao Liu, Xiao-Heng Li, Kai Li","doi":"10.1007/s12598-024-02820-8","DOIUrl":"https://doi.org/10.1007/s12598-024-02820-8","url":null,"abstract":"<p>CuW is widely used in high-voltage electrical switch contacts, rocket nozzle throat linings, electronic packaging materials and other major high-end technologies. CuW is typically fabricated using infiltration and high-temperature sintering methods based on powder metallurgy. As CuW composites fabricated using these methods have the disadvantages of low density and uneven microstructural distribution, the preparation of CuW composites by aluminothermic reduction was proposed. However, some Al<sub>2</sub>O<sub>3</sub> inclusions produced by aluminothermic reduction do not effectively combine with the slag-making agent CaO to form a liquid slag phase and remain in the CuW composite, resulting in a small number of Al<sub>2</sub>O<sub>3</sub> inclusions in the CuW composites. To overcome this problem, a novel methodology for strengthening metal-slag separation through in situ slagging is proposed. In this study, CuW composites were prepared by metallothermic reduction using Al, AlCa and AlMg as reducing agents. The CuW composites and slag samples were systematically analyzed. The results indicate that the Al<sub>2</sub>O<sub>3</sub> particles produced by aluminothermic reduction can be modified in situ into calcium aluminate and MgO·Al<sub>2</sub>O<sub>3</sub> with lower melting points by using AlCa and AlMg alloys as reducing agents, which strengthens the metal-slag separation. Moreover, AlCa and AlMg exhibited refining effects on the tungsten particles of the CuW composite, where the effect of AlMg was greater than that of AlCa. The slag obtained using the AlCa alloy as a reducing agent was mainly composed of CaWO<sub>4</sub>, CaAl<sub>4</sub>O<sub>7</sub> and Ca<sub>4</sub>Al<sub>6</sub>O<sub>12</sub>WO<sub>4</sub>, whereas that obtained using the AlMg alloy was mainly composed of CaWO<sub>4</sub>, MgAl<sub>2</sub>O<sub>4</sub> and Ca<sub>4</sub>Al<sub>6</sub>O<sub>12</sub>WO<sub>4</sub>.</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":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515742","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 : 2024-06-24DOI: 10.1007/s12598-024-02819-1
Shu-Bing Wei, Yong-Ju He, Yan Tang, Hong-Wei Fu, Jiang Zhou, Shu-Quan Liang, Xin-Xin Cao
Cost-efficient and high-performance cathodes play a crucial role in the advancement of grid-scale sodium-ion batteries (SIBs). As promising high-capacity cathode materials for SIBs, O3-type Na-based layered transition metal oxides constantly experience inadequate air stability and complex phase transitions. Herein, a comprehensive investigation was conducted to explore the impact of Ca substitution on both the electrochemical performance and structural stability of O3–Na1−2xCaxNi0.25Fe0.5Mn0.25O2 (x = 0, 0.02 and 0.05) that is proposed. With proper Ca content, O3-type Na0.96Ca0.02Ni0.25Fe0.5Mn0.25O2 can deliver a reversible capacity of 122.1 mAh·g−1 at 10 mA·g−1, with capacity retention of 83.4% after 200 cycles at 50 mA·g−1 and good rate capability. Its air sensitivity is investigated, and its potential as the Na host in full cells has been studied. In situ X-ray diffraction reveals the facilitated O3–P3–O3 phase transitions of such cathode during the whole electrochemical reaction. Such a simple and effective strategy may reveal a new avenue for high-stable O3-type cathodes and promote the practical applications of SIBs.
Graphical Abstract
高性价比和高性能的阴极对电网级钠离子电池（SIB）的发展起着至关重要的作用。作为有前景的高容量钠离子电池阴极材料，O3 型 Na 基层状过渡金属氧化物一直存在空气稳定性不足和相变复杂的问题。在此，我们进行了一项综合研究，探讨了 Ca 取代对所提出的 O3-Na1-2xCaxNi0.25Fe0.5Mn0.25O2 （x = 0、0.02 和 0.05）的电化学性能和结构稳定性的影响。在钙含量适当的情况下，O3 型 Na0.96Ca0.02Ni0.25Fe0.5Mn0.25O2 在 10 mA-g-1 下可提供 122.1 mAh-g-1 的可逆容量，在 50 mA-g-1 下循环 200 次后容量保持率为 83.4%，并具有良好的速率能力。研究人员对其空气敏感性进行了调查，并对其在全电池中作为 Na 宿主的潜力进行了研究。原位 X 射线衍射显示，这种阴极在整个电化学反应过程中促进了 O3-P3-O3 相变。这种简单有效的策略可能会为高稳定的 O3 型阴极开辟一条新的途径，并促进 SIB 的实际应用。
{"title":"A Ca-substituted air-stable layered oxide cathode material with facilitated phase transitions for high-performance Na-ion batteries","authors":"Shu-Bing Wei, Yong-Ju He, Yan Tang, Hong-Wei Fu, Jiang Zhou, Shu-Quan Liang, Xin-Xin Cao","doi":"10.1007/s12598-024-02819-1","DOIUrl":"https://doi.org/10.1007/s12598-024-02819-1","url":null,"abstract":"<p>Cost-efficient and high-performance cathodes play a crucial role in the advancement of grid-scale sodium-ion batteries (SIBs). As promising high-capacity cathode materials for SIBs, O<sub>3</sub>-type Na-based layered transition metal oxides constantly experience inadequate air stability and complex phase transitions. Herein, a comprehensive investigation was conducted to explore the impact of Ca substitution on both the electrochemical performance and structural stability of O<sub>3</sub>–Na<sub>1−2<i>x</i></sub>Ca<sub><i>x</i></sub>Ni<sub>0.25</sub>Fe<sub>0.5</sub>Mn<sub>0.25</sub>O<sub>2</sub> (<i>x</i> = 0, 0.02 and 0.05) that is proposed. With proper Ca content, O<sub>3</sub>-type Na<sub>0.96</sub>Ca<sub>0.02</sub>Ni<sub>0.25</sub>Fe<sub>0.5</sub>Mn<sub>0.25</sub>O<sub>2</sub> can deliver a reversible capacity of 122.1 mAh·g<sup>−1</sup> at 10 mA·g<sup>−1</sup>, with capacity retention of 83.4% after 200 cycles at 50 mA·g<sup>−1</sup> and good rate capability. Its air sensitivity is investigated, and its potential as the Na host in full cells has been studied. In situ X-ray diffraction reveals the facilitated O<sub>3</sub>–P<sub>3</sub>–O<sub>3</sub> phase transitions of such cathode during the whole electrochemical reaction. Such a simple and effective strategy may reveal a new avenue for high-stable O<sub>3</sub>-type cathodes and promote the practical applications of SIBs.</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":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515741","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 : 2024-06-24DOI: 10.1007/s12598-024-02824-4
Yang Liu, Ke Tan, Sen Liu, Xu Zhang, Mao-Qiang Shen, Xue-Sen Liu, Xin-Yue Gao, Lin-Rui Hou, Chang-Zhou Yuan
The shuttling diffusion of polysulfides is a bottleneck that seriously limits the performance of Li–S batteries. Purposeful construction of sulfur cathodes with reliable trapping ability of polysulfides is the key to overcome such limitation. Herein, a hierarchical porous architecture, i.e., Co(OH)2 sheets bonded Ti3C2Tx MXene aerogel (Co(OH)2/MXA), is constructed via a facile self-assembled approach and used as an efficient free-standing polysulfides reservoir. The interconnected three-dimensional (3D) porous network with void space and strong interfacial interaction not only enables high sulfur loading but facilitates fast ion and electron transport. Experimental and theoretical results confirm the hetero-framework exhibits outstanding immobilization and conversion ability for polysulfides due to its polar surface and bifunctional catalytic activities toward both formation and decomposition of Li2S. The optimized Co(OH)2/MXA cathode delivers excellent rate capability (407 mAh·g–1 at 5C) with a sulfur loading of 2.7 mg·cm−2, and ultra-stable cycling performance as an extremely small capacity decay of ~ 0.005% per cycle within 1700 cycles at 1C is achieved with a high sulfur loading of 6.7 mg·cm−2. More significantly, our design structural/componential methodology here promises the MXene-based aerogel electrodes for Li–S batteries and beyond.
{"title":"Self-assemble construction of hetero-structured Co(OH)2/MXene aerogel toward Li–S batteries as a self-supported host and bifunctional catalyst","authors":"Yang Liu, Ke Tan, Sen Liu, Xu Zhang, Mao-Qiang Shen, Xue-Sen Liu, Xin-Yue Gao, Lin-Rui Hou, Chang-Zhou Yuan","doi":"10.1007/s12598-024-02824-4","DOIUrl":"https://doi.org/10.1007/s12598-024-02824-4","url":null,"abstract":"<p>The shuttling diffusion of polysulfides is a bottleneck that seriously limits the performance of Li–S batteries. Purposeful construction of sulfur cathodes with reliable trapping ability of polysulfides is the key to overcome such limitation. Herein, a hierarchical porous architecture, i.e., Co(OH)<sub>2</sub> sheets bonded Ti<sub>3</sub>C<sub>2</sub>T<sub><i>x</i></sub> MXene aerogel (Co(OH)<sub>2</sub>/MXA), is constructed via a facile self-assembled approach and used as an efficient free-standing polysulfides reservoir. The interconnected three-dimensional (3D) porous network with void space and strong interfacial interaction not only enables high sulfur loading but facilitates fast ion and electron transport. Experimental and theoretical results confirm the hetero-framework exhibits outstanding immobilization and conversion ability for polysulfides due to its polar surface and bifunctional catalytic activities toward both formation and decomposition of Li<sub>2</sub>S. The optimized Co(OH)<sub>2</sub>/MXA cathode delivers excellent rate capability (407 mAh·g<sup>–1</sup> at 5C) with a sulfur loading of 2.7 mg·cm<sup>−2</sup>, and ultra-stable cycling performance as an extremely small capacity decay of ~ 0.005% per cycle within 1700 cycles at 1C is achieved with a high sulfur loading of 6.7 mg·cm<sup>−2</sup>. More significantly, our design structural/componential methodology here promises the MXene-based aerogel electrodes for Li–S batteries and beyond.</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":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515739","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 : 2024-06-24DOI: 10.1007/s12598-024-02746-1
Cheng-Zhang Zhu, Qi-Hang Tian, Bing-Han Wang, Mu-Tao Xu, Qi-Jie Jin, Zi-Ye Zhang, Shu-Kun Le, Yang Wu, Yue-Chang Wei, Hai-Tao Xu
Cerium dioxide (CeO2) is a significant rare earth oxide with the merits of rich oxygen defects, specific 4f15d1 orbitals, and superior oxygen storage-release capacity in Ce4+/Ce3+ reversibility pairs, and has been widely investigated as an active photocatalytic material for air pollution remediation. To enhance the photocatalytic efficiency of CeO2, recent developments of numerous modification strategies have been employed to broaden the light absorption range and reduce the recombination rate of electron–hole pairs. This review summarizes the fabrication of modified CeO2 catalysts, including metal or nonmetal doping, heterostructure construction and oxygen vacancy manufacturing, to provide insight into how those advanced techniques improve the photocatalytic activity. Moreover, this work provides a detailed discussion on the usage of modified CeO2 in the fields of air pollution control, including nitrogen oxides removal, volatile organic compounds elimination and the purification of carbon dioxide. Finally, the potential future development and further research on the modification of CeO2 has been identified.
{"title":"Application of modified cerium dioxide for photocatalytic air pollution purification","authors":"Cheng-Zhang Zhu, Qi-Hang Tian, Bing-Han Wang, Mu-Tao Xu, Qi-Jie Jin, Zi-Ye Zhang, Shu-Kun Le, Yang Wu, Yue-Chang Wei, Hai-Tao Xu","doi":"10.1007/s12598-024-02746-1","DOIUrl":"https://doi.org/10.1007/s12598-024-02746-1","url":null,"abstract":"<p>Cerium dioxide (CeO<sub>2</sub>) is a significant rare earth oxide with the merits of rich oxygen defects, specific 4f<sup>1</sup>5d<sup>1</sup> orbitals, and superior oxygen storage-release capacity in Ce<sup>4+</sup>/Ce<sup>3+</sup> reversibility pairs, and has been widely investigated as an active photocatalytic material for air pollution remediation. To enhance the photocatalytic efficiency of CeO<sub>2</sub>, recent developments of numerous modification strategies have been employed to broaden the light absorption range and reduce the recombination rate of electron–hole pairs. This review summarizes the fabrication of modified CeO<sub>2</sub> catalysts, including metal or nonmetal doping, heterostructure construction and oxygen vacancy manufacturing, to provide insight into how those advanced techniques improve the photocatalytic activity. Moreover, this work provides a detailed discussion on the usage of modified CeO<sub>2</sub> in the fields of air pollution control, including nitrogen oxides removal, volatile organic compounds elimination and the purification of carbon dioxide. Finally, the potential future development and further research on the modification of CeO<sub>2</sub> has been identified.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":8.8,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515740","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}
Direct electrochemical conversion of NO to NH3 has attracted widespread interest as a green and sustainable strategy for both ammonia synthesis and nitric oxide removal. However, designing efficient catalysts remains challenging due to the complex reaction mechanism and competing side reactions. Single-atom alloy (SAA) catalysts, which increase the atomic efficiency and the chance to tailor the electronic properties of the active center, have become a frontier in this field. Here, we performed a systematic screening of transition metal-doped Au SAAs (denoted as TM/Au, TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag and Pt) to find potential catalysts for electrochemical NO reduction reaction (NORR) to NH3. By employing a four-step screening strategy based on density functional theory (DFT) calculations, Zn/Au SAA has been identified as a promising NORR catalyst due to its superior structural stability, reaction activity and NH3 selectivity. The electron-involved steps on Zn/Au are thermodynamically spontaneous, which results in a positive limiting potential (UL) of 0.15 V. The preferred NO affinity compared to H adatom demonstrates that Zn/Au can effectively suppress the hydrogen evolution reaction. Machine-learning (ML) investigations were adopted to address the uncertainty between the physicochemical properties of SAAs and the NORR performance. We applied an extreme gradient boosting regression (XGBR) algorithm to predict the limiting potentials in terms of the intrinsic features of the reaction site. The coefficient of determination (R2) is 0.97 for the training set and 0.96 for the test set. The electronic structure analysis combined with a compressed-sensing data-analytics approach further quantitatively verifies the coeffect of d-band center, charge transfer and the radius of doped TM atoms, i.e., features with the highest level of importance determined by the XGBR algorithm. This work provides a theoretical understanding of the complex NORR to NH3 mechanisms and sheds light on the rational design of SAA catalysts by combining DFT and ML investigations.
Graphical abstract
将 NO 直接电化学转化为 NH3 作为一种绿色、可持续的合成氨和去除一氧化氮的策略引起了广泛关注。然而，由于复杂的反应机理和相互竞争的副反应，设计高效催化剂仍具有挑战性。单原子合金（SAA）催化剂提高了原子效率，并有机会定制活性中心的电子特性，已成为该领域的前沿技术。在此，我们对掺杂过渡金属的金 SAA（表示为 TM/Au，TM = Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ru、Rh、Pd、Ag 和 Pt）进行了系统筛选，以寻找将 NO 还原成 NH3 的电化学还原反应（NORR）的潜在催化剂。通过采用基于密度泛函理论（DFT）计算的四步筛选策略，Zn/Au SAA 因其优异的结构稳定性、反应活性和 NH3 选择性而被确定为一种有前途的 NORR 催化剂。Zn/Au 上的电子参与步骤在热力学上是自发的，这导致了 0.15 V 的正极限电位 (UL)。我们采用了机器学习（ML）研究来解决 SAAs 的物理化学特性与 NORR 性能之间的不确定性。我们采用极端梯度提升回归（XGBR）算法，根据反应场所的内在特征来预测极限电位。训练集的判定系数 (R2) 为 0.97，测试集的判定系数 (R2) 为 0.96。电子结构分析与压缩感应数据分析方法相结合，进一步定量验证了 d 波段中心、电荷转移和掺杂 TM 原子半径的协同效应，即 XGBR 算法确定的重要性最高的特征。这项工作从理论上理解了复杂的 NORR 转化为 NH3 的机理，并通过结合 DFT 和 ML 研究，为合理设计 SAA 催化剂提供了启示。
{"title":"Machine-learning-aided Au-based single-atom alloy catalysts discovery for electrochemical NO reduction reaction to NH3","authors":"Hui-Long Jin, Qian-Nan Li, Yun-Yan Tian, Shuo-Ao Wang, Xing Chen, Jie-Yu Liu, Chang-Hong Wang","doi":"10.1007/s12598-024-02833-3","DOIUrl":"https://doi.org/10.1007/s12598-024-02833-3","url":null,"abstract":"<p>Direct electrochemical conversion of NO to NH<sub>3</sub> has attracted widespread interest as a green and sustainable strategy for both ammonia synthesis and nitric oxide removal. However, designing efficient catalysts remains challenging due to the complex reaction mechanism and competing side reactions. Single-atom alloy (SAA) catalysts, which increase the atomic efficiency and the chance to tailor the electronic properties of the active center, have become a frontier in this field. Here, we performed a systematic screening of transition metal-doped Au SAAs (denoted as TM/Au, TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag and Pt) to find potential catalysts for electrochemical NO reduction reaction (NORR) to NH<sub>3</sub>. By employing a four-step screening strategy based on density functional theory (DFT) calculations, Zn/Au SAA has been identified as a promising NORR catalyst due to its superior structural stability, reaction activity and NH<sub>3</sub> selectivity. The electron-involved steps on Zn/Au are thermodynamically spontaneous, which results in a positive limiting potential (<i>U</i><sub>L</sub>) of 0.15 V. The preferred NO affinity compared to H adatom demonstrates that Zn/Au can effectively suppress the hydrogen evolution reaction. Machine-learning (ML) investigations were adopted to address the uncertainty between the physicochemical properties of SAAs and the NORR performance. We applied an extreme gradient boosting regression (XGBR) algorithm to predict the limiting potentials in terms of the intrinsic features of the reaction site. The coefficient of determination (<i>R</i><sup>2</sup>) is 0.97 for the training set and 0.96 for the test set. The electronic structure analysis combined with a compressed-sensing data-analytics approach further quantitatively verifies the coeffect of d-band center, charge transfer and the radius of doped TM atoms, i.e., features with the highest level of importance determined by the XGBR algorithm. This work provides a theoretical understanding of the complex NORR to NH<sub>3</sub> mechanisms and sheds light on the rational design of SAA catalysts by combining DFT and ML investigations.</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":"2024-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141508592","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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