Science China Chemistry最新文献

{"title":"Upcycling of polyphenylene oxide into 2,6-dimethyl aniline via depolymerization and amination over a Pt/CeO2 catalyst","authors":"Shengchao Jia, Wenke Zhao, Xiaohui Liu, Yong Guo, Yanqin Wang","doi":"10.1007/s11426-024-2278-9","DOIUrl":"https://doi.org/10.1007/s11426-024-2278-9","url":null,"abstract":"<p>Upcycling of plastic waste into N-containing compound is a novel and attractive strategy for its disposal and will opens up a promising direction for the production of value-added amines. Herein, an efficient strategy for the depolymerization-amination of polyphenylene oxide (PPO) into 2,6-dimethyl aniline is developed over a simple Pt/CeO₂ catalyst. The C–O linkages of PPO can be selectively broken, producing 2,6-dimethyl phenol and then hydrogenated and aminated to 2,6-dimethyl cyclohexylamine over the Pt/CeO₂ catalyst. Finally, 2,6-dimethyl aniline was produced with high selectivity through the dehydrogenation of 2,6-dimethyl cyclohexylamine in the same catalyst. Toluene can be used as the hydrogen-acceptor in the dehydrogenation step and enhance the selectivity of target product. Single N-containing compound, 2,6-dimethyl aniline, is obtained and separated after HCl treatment. Meanwhile, the Pt/CeO₂ catalyst exhibit remarkable stability and can sustainably catalyze the synthesis of 2,6-dimethyl aniline in several cycles.</p>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"27 1","pages":""},"PeriodicalIF":9.445,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142197161","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Durable ruthenium oxide catalysts for water oxidation reaction","authors":"Jixiang Jiao, Ding Chen, Hongyu Zhao, Ying Dong, Shichun Mu","doi":"10.1007/s11426-024-2227-2","DOIUrl":"https://doi.org/10.1007/s11426-024-2227-2","url":null,"abstract":"<p>Water electrolysis is an important way for high-purity hydrogen production. However, the oxygen evolution reaction (OER), as a key reaction, has a high energy barrier, and the associated catalyst is prone to failure. Therefore, efficient and stable OER catalysts are urgently required. Compared with commercial iridium oxide (IrO₂), ruthenium oxide (RuO₂) has a lower price and higher catalytic activity for OER due to its location at the near-top of the volcano plot, but has lower structural stability. Thus, an in-depth understanding of the failure mechanism of RuO₂ is conducive to the reaction pathway design and structural modulation for obtaining higher stable RuO₂ catalysts. Here, we discuss recent advances in the enhancement of the stability of RuO₂ catalysts. First, we analyze in depth the three failure modes of RuO₂, including the oxidation of Ru, the lattice oxygen evolution, and the catalyst exfoliation during the OER process. Second, to improve the durability of RuO₂ catalysts, five modification strategies, comprising defective engineering, strain engineering, phase engineering, interface engineering and microenvironmental engineering, are summarized, and corresponding enhancement mechanisms are also discussed. Finally, the challenges and possible solutions for further breakthroughs of RuO₂ catalysts are proposed, and the future research trends and prospects of RuO₂ catalysts are also envisioned. Undoubtedly, this work will contribute to the understanding and design of highly stable OER catalysts and beyond.</p>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"495 1","pages":""},"PeriodicalIF":9.445,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142225140","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An NIR-II-emissive Ru(II) metallacycle for efficient and safe immunotherapy","authors":"Chonglu Li,&nbsp;Jianbo Zhan,&nbsp;Biao Dong","doi":"10.1007/s11426-024-2193-5","DOIUrl":"10.1007/s11426-024-2193-5","url":null,"abstract":"","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 1","pages":"5 - 7"},"PeriodicalIF":10.4,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925512","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhancing solid-state lithium metal battery performance via indium-based modification of electrolytes and lithium metal surfaces: mechanistic insights and optimization","authors":"Zhongkai Wu, Chen Liu, Ziling Jiang, Lin Li, Siwu Li, Chaochao Wei, Qiyue Luo, Xia Chen, Long Zhang, Shijie Cheng, Chuang Yu","doi":"10.1007/s11426-024-2275-2","DOIUrl":"https://doi.org/10.1007/s11426-024-2275-2","url":null,"abstract":"<p>Argyrodite-based solid-state lithium metal batteries exhibit significant potential as next-generation energy storage devices. However, their practical applications are constrained by the intrinsic poor stability of argyrodite towards Li metal and exposure to air/moisture. Therefore, an indium-involved modification strategy is employed to address these issues. The optimized doping yields a high Li-ion conductivity of 7.5 mS cm⁻¹ for Li_5.54In_0.02PS_4.47O_0.03Cl_1.5 electrolyte, accompanied by enhanced endurance against air/moisture and bare Li metal. It retains 92.0% of its original conductivity after exposure to air at a low dew point of −60 °C in dry room. Additionally, a composite layer comprising Li–In alloy and LiF phases is generated on the surface of lithium metal anode via the reaction between InF₃ and molten Li. This layer effectively mitigates Li dendrite growth by creating a physical barrier from the robust LiF phase, while the Li–In alloy induces uniform Li-ion deposition and accelerates Li transport dynamics across the interphase between the solid electrolyte/Li metal. Moreover, the In-doped electrolyte facilitates the <i>in-situ</i> generation of Li–In alloy within its voids, reducing local current density and further inhibiting lithium dendrite growth. Consequently, the combination of the Li_5.54In_0.02PS_4.47O_0.03Cl_1.5 electrolyte and the InF₃@Li anode provides exceptional electrochemical performances in both symmetric cells and solid-state lithium metal batteries across different operating temperatures. Specifically, the LiNbO₃@LiNi_0.7Co_0.2Mn_0.1O₂/Li_5.54In_0.02PS_4.47O_0.03Cl_1.5/InF₃@Li cell delivers a high discharge capacity of 167.8 mAh g⁻¹ at 0.5 C under 25 °C and retains 80.0% of its initial value after 400 cycles. This work offers a viable strategy for designing functional interfaces with enhanced stability for sulfide-based solid-state lithium batteries.</p>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"87 1","pages":""},"PeriodicalIF":9.445,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142197169","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unraveling the catalytic redox mechanism of lithium–sulfur batteries through advanced in-situ/operando characterizations","authors":"Pan Zeng, Cheng Yuan, Bin Su, Genlin Liu, Jiechang Gao, Kun Yang, Qingyuan Wang, Liang Zhang","doi":"10.1007/s11426-024-2219-x","DOIUrl":"https://doi.org/10.1007/s11426-024-2219-x","url":null,"abstract":"<p>Accelerating the redox conversion of lithium polysulfides (LiPSs) with electrocatalysts has been regarded as an effective avenue to surmount the shuttle effect and realize high-performance lithium–sulfur (Li–S) batteries. However, the complicated reaction process, especially the real-time evolution of sulfur-containing species and electrocatalysts under working conditions, has brought great difficulties in the explicit understanding of reaction mechanism of Li–S batteries, thereby severely hampering the design of highly efficient electrocatalysts. Therefore, a crucial prerequisite for correctly identifying the reaction mechanism is an in-depth analysis of the dynamic evolution of reaction intermediates and their structure-performance relationships. In this review, we comprehensively summarized the most recent progress in the dynamic behaviors of LiPSs and electrocatalysts of Li–S batteries under working conditions in conjunction with closely related <i>in-situ/operando</i> characterizations to recognize the realtime evolution of phase, composition, and atomic/electronic structure, thereby unraveling the corresponding catalytic mechanism. In addition, the major challenges and unexplored issues of catalytic conversion of LiPSs were summarized and discussed, aiming to provide perspectives into the development of highly efficient electrocatalysts in Li–S chemistry. Based on this review, we believe that reasonable regulation of reconstruction behaviors can achieve satisfactory electrocatalysts with high catalytic activity, accelerating the development of green energy.</p>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"60 1","pages":""},"PeriodicalIF":9.445,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142225138","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chemical warfare agent countermeasures based on macrocycle supramolecular chemistry","authors":"Junyi Chen, Yahan Zhang, Chunju Li, Qingbin Meng","doi":"10.1007/s11426-024-2217-9","DOIUrl":"https://doi.org/10.1007/s11426-024-2217-9","url":null,"abstract":"<p>Given that chemical warfare agents (CWAs) pose some of the largest threats to humankind, social stability, and world peace, considerable attention has been drawn to the development of the corresponding detection, decontamination, and treatment techniques. The versatile functionality and distinctive recognition potency of macrocycles enable their customized design for specific tasks, such as chemical sensing, catalysis, or separation. Hence, supramolecular materials are well suited for the establishment of CWA countermeasures. Herein, we summarize the recent progress in the development of macrocycle-based materials for counteracting several representative CWAs, including nerve, blister, blood, incapacitating, choking, and irritating agents, providing a foundation for further advances in this field and fostering practical translational terms.</p>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"11 1","pages":""},"PeriodicalIF":9.445,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142197166","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Efficient epoxidation of propylene over non-noble nickel-based catalyst promoted by alkali metals","authors":"Wenqian Li,&nbsp;Wanting Li,&nbsp;Xinxin Cao,&nbsp;Longfei Chen,&nbsp;Yibo Qin,&nbsp;Yanfeng Zhu,&nbsp;Yanfei Zhang,&nbsp;Gai Miao,&nbsp;Lingzhao Kong,&nbsp;Jiong Li,&nbsp;Xinqing Chen","doi":"10.1007/s11426-024-2161-9","DOIUrl":"10.1007/s11426-024-2161-9","url":null,"abstract":"<div><p>The application of non-noble metal catalysts in the catalytic direct gas-phase epoxidation of propylene with H₂ and O₂ to produce propylene oxide is valuable and challenging. The introduction of alkali metal promoters is one of the effective methods to improve the catalytic activity of catalysts. Herein, a series of alkali metal (Li, Na, K, Rb, and Cs)-promoted Ni/TS-1 catalysts were prepared to deeply understand the effect of alkali metals on the structure-activity relationship for gas-phase epoxidation of propylene. Among them, the Na-Ni/TS-1 catalyst exhibits the highest catalytic activity (propylene conversion of 7.35% and PO formation rate of 157.9 g h⁻¹ kg_cat⁻¹) and the best stability (long-term stability exceeding 140 h at 200 °C). X-ray absorption and photoelectron spectroscopy revealed that the electronic structure of Ni can be tuned by the addition of alkali metal promoters. NH₃-TPD-MS, CO₂-TPD-MS, and C₃H₆-TPD-MS results indicate that the acidity of the catalyst can also be adjusted by the introduction of alkali metal, whereas the Na-Ni/TS-1 catalyst exhibits the strongest C₃H₆ adsorption capacity. Thus, the suitable acid-base properties, unique electronic properties of Ni species, and the strongest propylene adsorption capacity resulted in improved propylene gas-phase epoxidation activity of Na-Ni/TS-1 catalyst. This study not only provides a new strategy for the practical application of nickel-based catalysts in the gas-phase epoxidation of propylene but also provides insights into the promoting effect of alkali metals.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"67 11","pages":"3697 - 3705"},"PeriodicalIF":10.4,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11426-024-2161-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142197170","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Homogeneous permeation and oriented crystallization in nanostructured mesopores for efficient and stable printable mesoscopic perovskite solar cells","authors":"Guodong Zhang,&nbsp;Yanjie Cheng,&nbsp;Tingting Niu,&nbsp;Ziwei Zheng,&nbsp;Zongwei Li,&nbsp;Junwei Xiang,&nbsp;Qiaojiao Gao,&nbsp;Minghao Xia,&nbsp;Lijuan Guo,&nbsp;Yiming Liu,&nbsp;Mengru Zhang,&nbsp;Yiran Tao,&nbsp;Xueqin Ran,&nbsp;Mingjie Li,&nbsp;Guichuan Xing,&nbsp;Yingdong Xia,&nbsp;Lingfeng Chao,&nbsp;Anyi Mei,&nbsp;Hongwei Han,&nbsp;Yonghua Chen","doi":"10.1007/s11426-024-2283-9","DOIUrl":"10.1007/s11426-024-2283-9","url":null,"abstract":"<div><p>The low-cost and scalable printable mesoporous perovskite solar cells (p-MPSCs) face significant challenges in regulating perovskite crystal growth due to their nanoscale mesoporous scaffold structure, which limits the improvement of device power conversion efficiency (PCE). In particular, the most commonly used solvents, <i>N,N</i>-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), have a single chemical interaction with the precursor components and high volatility, which is insufficient to self-regulate the perovskite crystallization process, leading to explosive nucleation and limited growth within mesoporous scaffolds. Here, we report a mixed solvent system composed of methylamine formaldehyde (MAFa)-based ionic liquid and acetonitrile (ACN) with the strong C=O–Pb coordination and N–H⋯I hydrogen bonding with perovskite components. We found that the mixed solvent system is beneficial for the precursor solution to homogeneously penetrate into the mesoporous scaffold, and the strong C=O–Pb coordination and N–H⋯I hydrogen bonding interaction can promote the oriented growth of perovskite crystals. This synergistic effect increased the PCE of the p-MPSCs from 17.50% to 19.21%, which is one of the highest records for p-MPSC in recent years. Additionally, the devices exhibit positive environmental stability, retaining over 90% of the original PCE after 1,200 h of aging under AM 1.5 illumination conditions at 55 °C and 55% humidity.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"67 11","pages":"3688 - 3696"},"PeriodicalIF":10.4,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142197168","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electronic structure tuning of layered double hydroxides for electrochemical sensing and its biomedical applications","authors":"Kun Wang,&nbsp;Zhiying Cao,&nbsp;Qihang Ding,&nbsp;Jiyoung Yoo,&nbsp;Nem Singh,&nbsp;Heemin Kang,&nbsp;Lin Wang,&nbsp;Lin Xu,&nbsp;Jong Seung Kim","doi":"10.1007/s11426-024-2215-y","DOIUrl":"10.1007/s11426-024-2215-y","url":null,"abstract":"<div><p>Modifying the electrodes of electrochemical sensors is critical to enhance sensitivity, selectivity, and stability, ultimately improving both their effectiveness and performance. In this paper, recent advancements in electrochemical sensors are reviewed, focusing on the utilization of layered double hydroxides (LDHs). The first section explores the advantageous and disadvantageous aspects of electrochemical sensing. Benefits include rapid response, ease of operation, and cost-effectiveness, while drawbacks concern the potential instability of prolonged use, susceptibility to interference, and the risk of biomolecule inactivation. Following this, the second section delves into the synthesis, constituents, and structure of LDHs. Moreover, after introducing the chemical mechanisms and functions of LDHs in electrochemical sensors, we concentrate on diverse modifying materials of LDHs and their different performances. Finally, the applications of LDHs in electrochemical sensing across different fields are discussed. This review aims to facilitate the continued advancement for applying LDHs in electrochemical sensors, as well as inspire the evolution of electrochemical sensing technology.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"67 11","pages":"3614 - 3630"},"PeriodicalIF":10.4,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142225139","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of ordered mesoporous crystalline boron phosphate scaffold with double diamond surface structure","authors":"Chao Wang, Wen-Duo Lu, Jiao Wang, Shunai Che, An-Hui Lu, Lu Han","doi":"10.1007/s11426-024-2221-8","DOIUrl":"https://doi.org/10.1007/s11426-024-2221-8","url":null,"abstract":"<p>Ordered mesoporous materials have received great attention due to their well-defined pore structures and potential applications in catalysis, adsorption, separation, drug delivery, etc. Although various compositions of mesoporous solids have been successfully prepared, the preparation of crystalline non-metallic oxyacid salts with ordered mesoporosity remains a major challenge. Herein, we report the synthesis of a mesoporous solid acid crystalline boron phosphate (BPO₄) catalyst with a bicontinuous shifted double diamond (SDD) hyperbolic surface structure. The BPO₄ scaffold was obtained by synergistic self-assembly in a mixed solvent of water and tetrahydrofuran using the diblock copolymer poly(ethylene oxide)-<i>block</i>-polystyrene as template and phosphoric acid and orthoboric acid as inorganic sources. The structure consists of two sets of diamond networks adjacent to each other with a mesostructural scale tetragonal symmetry (space group <i>I</i>4₁/<i>amd</i>) with unit cell parameters of <i>a</i> = 80 nm and <i>c</i> = 113 nm, which affords the scaffold a specific surface area of 44 m²/g. As a solid acid catalytic material, the SDD BPO₄ scaffold exhibited excellent catalytic activity at room temperature with a conversion of furfural to 2-(dimethoxymethyl) furan over 70% and can be reused after recovery without serious loss of activity. In the propane oxidative dehydrogenation reaction, SDD BPO₄ demonstrated high olefin productivity and selectivity while maintaining high reaction rate. This study provides ideas for the preparation of ordered mesoporous crystalline catalytic materials and demonstrates their potential for practical applications.</p>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"11 1","pages":""},"PeriodicalIF":9.445,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142197176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}