Industrial Chemistry & Materials最新文献

{"title":"Recent progress in metal–organic frameworks (MOFs) for electrocatalysis","authors":"Cha Li, Hao Zhang, Ming Liu, Fei-Fan Lang, Jiandong Pang and Xian-He Bu","doi":"10.1039/D2IM00063F","DOIUrl":"https://doi.org/10.1039/D2IM00063F","url":null,"abstract":"<p>Electrocatalytic technology opens a new path to solve the existing problems in fossil fuel consumption and environmental pollution as well as efficient energy use. Metal–organic frameworks (MOFs), a class of crystalline porous materials with high specific surface area, high porosity and customizable structures, have emerged as promising electrocatalysts. However, their inherently low electrical conductivity and stability greatly hinder their further applications. Therefore, strategies such as synthesizing two-dimensional conductive MOFs, designing unsaturated metal sites, and building MOF nanoarrays have been developed to enhance the conductivity and catalytic reaction transfer rates of MOFs, accompanied by the rational designs of MOFs for improving their stability. In this review, the applications of MOF-based electrocatalysts in the hydrogen evolution reaction (HER), hydrogen oxidation reaction (HOR), oxygen evolution reaction (OER), oxygen reduction reaction (ORR) and nitrogen reduction reaction (NRR) are presented in detail with the classification of monometallic MOFs, bimetallic MOFs, MOF-based composites and MOFs as supports. In addition, the relationship between the structure and performance is discussed through DFT calculations used in related work. Finally, future challenges and application prospects of MOFs in electrocatalysis are highlighted.</p><p>Keywords: Metal–organic frameworks; Electrocatalyst; Catalytic performance; Catalysis; Energy conversion.</p>","PeriodicalId":29808,"journal":{"name":"Industrial Chemistry & Materials","volume":" 1","pages":" 9-38"},"PeriodicalIF":0.0,"publicationDate":"2023-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/im/d2im00063f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49994634","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ionic liquid/poly(ionic liquid)-based electrolytes for lithium batteries","authors":"Xinyu Ma, Jiangtao Yu, Yin Hu, John Texter and Feng Yan","doi":"10.1039/D2IM00051B","DOIUrl":"https://doi.org/10.1039/D2IM00051B","url":null,"abstract":"<p>The growing demand for portable electronic devices, electric vehicles, and large-scale advanced energy storage has aroused increasing interest in the development of high energy density lithium batteries. The electrolyte is an important component of lithium batteries and is an essential part of performance and safety improvements. Commercially available electrolytes mainly consist of lithium salts and organic carbonate solvents that are prone to decomposition due to their narrow electrochemical windows and tend to react with lithium metal anodes forming an unstable solid electrode/electrolyte interface (SEI). In particular, the flammability of organic solvents raises concerns about battery safety. Ionic liquid/poly(ionic liquid) (IL/PIL)-based electrolytes enable batteries with good safety, high energy/power density and long-term stability. This review focuses on the applications of IL/PIL-based liquid, quasi-solid, and solid electrolytes and electrolyte additives in lithium batteries. The perspectives and challenges of IL/PIL electrolytes in the field of lithium batteries are also proposed.</p><p>Keywords: Ionic liquid; Poly(ionic liquid); Lithium battery; Solid electrolyte; Quasi-solid electrolyte; Additive.</p>","PeriodicalId":29808,"journal":{"name":"Industrial Chemistry & Materials","volume":" 1","pages":" 39-59"},"PeriodicalIF":0.0,"publicationDate":"2023-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/im/d2im00051b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49994731","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Co and Ni single sites on the (111)n surface of γ-Al2O3 – a periodic boundary DFT study†","authors":"Jiande Gu, Jing Wang and Jerzy Leszczynski","doi":"10.1039/D2IM00039C","DOIUrl":"https://doi.org/10.1039/D2IM00039C","url":null,"abstract":"<p>The influences of increasing the number of d-electrons in the single metal (Fe-like) substituted (111)<small>_<em>n</em></small> surface of γ-Al<small>₂</small>O<small>₃</small> on its possible catalytic effects were explored. The energetic properties, local structures, and in-site electron configurations of the most active tri-coordinated Co and Ni single-site (111)<small>_<em>n</em></small> surface of γ-Al<small>₂</small>O<small>₃</small> have been studied using the density functional theory (DFT) approach under periodic boundary conditions. The replacement of Al by a Co or Ni atom on the I position of the (111)<small>_<em>n</em></small> surface leads to significant elongations of metal–O distances. The energy released from the substitution process on the Al<small>_I</small> site of the (111)<small>_<em>n</em></small> surface follows the sequence Ni<small>_I</small> (164.85 kcal mol<small>⁻¹</small>) &gt; Co<small>_I</small> (113.17 kcal mol<small>⁻¹</small>) &gt; Fe<small>_I</small> (44.30 kcal mol<small>⁻¹</small>). The triplet and quintet (ground state) of the Co<small>_I</small> substituted complex are energy degenerate. Also, the doublet and quartet (ground state) of the Ni<small>_I</small> substituted complex have the same stable energy. This energy degeneracy comes from the α–β electron flipping on the p-orbital of the neighboring O that is next to the substituted Co<small>_I</small> or Ni<small>_I</small> site on the (111)<small>_<em>n</em></small> surface of γ-Al<small>₂</small>O<small>₃</small>. Different from the Fe<small>_I</small> substituted single-site (111)<small>_<em>n</em></small> surface, in which the electron configuration of Fe<small>_I</small> varies according to its spin-multiplicity state, substituted Ni<small>_I</small> has a unique d<small>⁸</small> electron configuration in all three spin states, and similarly, Co<small>_I</small> has a unique d<small>⁷</small> electron configuration in all three open shell spin states. An increase of the population of d-electrons in the single metal substituted (111)<small>_<em>n</em></small> surface of γ-Al<small>₂</small>O<small>₃</small> is likely to provide a more stable electron configuration in the metal catalytic center.</p><p>Keywords: Co substituted surface of γ-Al<small>₂</small>O<small>₃</small>; Ni substituted surface of γ-Al<small>₂</small>O<small>₃</small>; (111)<small>_<em>n</em></small> surface; Periodic boundary DFT approach; Metal catalytic center.</p>","PeriodicalId":29808,"journal":{"name":"Industrial Chemistry & Materials","volume":" 1","pages":" 117-128"},"PeriodicalIF":0.0,"publicationDate":"2023-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/im/d2im00039c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49995212","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical insights into NH3 absorption mechanisms with imidazolium-based protic ionic liquids†","authors":"Wenhui Tu, Shaojuan Zeng, Yinge Bai, Xiaochun Zhang, Haifeng Dong and Xiangping Zhang","doi":"10.1039/D2IM00041E","DOIUrl":"https://doi.org/10.1039/D2IM00041E","url":null,"abstract":"<p>Ionic liquids (ILs) provide a promising way for efficient absorption and separation of ammonia (NH<small>₃</small>) due to their extremely low vapor pressures and adjustable structures. However, the understanding of absorption mechanisms especially in terms of theoretical insights is still not very clear, which is crucial for designing targeted ILs. In this work, a universal method that integrates density functional theory and molecular dynamic simulations was proposed to study the mechanisms of NH<small>₃</small> absorption by protic ionic liquids (PILs). The results showed that the NH<small>₃</small> absorption performance of the imidazolium-based PILs ([BIm][X], X= Tf<small>₂</small>N, SCN and NO<small>₃</small>) is determined by not only the hydrogen bonding between the N atom in NH<small>₃</small> and the protic site (H–N<small>³</small>) on the cation but also the cation–anion interaction. With the increase in NH<small>₃</small> absorption capacity, the hydrogen bonding between [BIm][Tf<small>₂</small>N] and NH<small>₃</small> changed from orbital dominated to electrostatic dominated, so 3.0 mol NH<small>₃</small> per mol IL at 313.15 K and 0.10 MPa was further proved as a threshold for NH<small>₃</small> capacity of [BIm][Tf<small>₂</small>N] by the Gibbs free energy results, which agrees well with the experimental results. Furthermore, the anions of [BIm][X] could also compete with NH<small>₃</small> for interaction with H-N<small>³</small> of the cation, which weakens the interaction between the cation and NH<small>₃</small> and then decreases the NH<small>₃</small> absorption ability of PILs. This study provides further understanding on NH<small>₃</small> absorption mechanisms with ILs, which will guide the design of novel functionalized ILs for NH<small>₃</small> separation and recovery.</p><p>Keywords: Protic ionic liquids; NH<small>₃</small> absorption; Interaction mechanisms; Simulation calculations.</p>","PeriodicalId":29808,"journal":{"name":"Industrial Chemistry & Materials","volume":" 2","pages":" 262-270"},"PeriodicalIF":0.0,"publicationDate":"2023-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/im/d2im00041e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49994119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Poly(alkyl-biphenyl pyridinium) anion exchange membranes with a hydrophobic side chain for mono-/divalent anion separation†","authors":"Hongxin Yang, Noor Ul Afsar, Qian Chen, Xiaolin Ge, Xingya Li, Liang Ge and Tongwen Xu","doi":"10.1039/D2IM00043A","DOIUrl":"https://doi.org/10.1039/D2IM00043A","url":null,"abstract":"<p>A series of poly(alkyl-biphenyl pyridinium) anion exchange membranes (AEMs) with a hydrophobic side chain were prepared for mono-/divalent anion separation using electrodialysis (ED). A poly(alkyl-biphenyl pyridinium) polymer was synthesized <em>via</em> superacid-catalyzed polymerization, and then quaternization was conducted using Menshutkin reactions with 1-bromopentane. The obtained quaternized product had excellent solubility in common organic solvents, making it flexible to form homogeneous membranes by a solution casting method. The introduction of a hydrophobic side chain resulted in a microphase separation structure in the membrane, which is favorable to the active transport of Cl<small>⁻</small> (higher Cl<small>⁻</small> flux of up to 3.37 mol m<small>⁻²</small> h<small>⁻¹</small> at a 10 mA cm<small>⁻²</small> current density) compared with that of SO<small>₄</small><small>²⁻</small> ions giving a high permselectivity of 11.9 in a mixed salt (NaCl/Na<small>₂</small>SO<small>₄</small>) system. In addition, the prepared membrane exhibited excellent alkaline stability in successive ED tests. It showed an OH<small>⁻</small> flux of up to 3.6 mol m<small>⁻²</small> h<small>⁻¹</small> with a permselectivity of 361.2 between OH<small>⁻</small> and WO<small>₄</small><small>²⁻</small>, which is much higher than that of Neosepta ACS membrane. The ED results manifest that the poly(alkyl-biphenyl pyridinium) AEMs can be promising candidates for practical mono-/divalent anion separation in industry.</p><p>Keywords: Superacid-catalyzed polymerization; Anion exchange membrane; Mono-/divalent anion separation; Electrodialysis; Permselectivity.</p>","PeriodicalId":29808,"journal":{"name":"Industrial Chemistry & Materials","volume":" 1","pages":" 129-139"},"PeriodicalIF":0.0,"publicationDate":"2023-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/im/d2im00043a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49994177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multicomponent catalyst design for CO2/N2/NOx electroreduction","authors":"Shunhan Jia, Limin Wu, Liang Xu, Xiaofu Sun and Buxing Han","doi":"10.1039/D2IM00056C","DOIUrl":"https://doi.org/10.1039/D2IM00056C","url":null,"abstract":"<p>Electroreduction of small molecules such as CO<small>₂</small>, N<small>₂</small>, and NO<small>₃</small><small>⁻</small> is one of the promising routes to produce sustainable chemicals and fuels and store renewable energy, which could contribute to our carbon neutrality goal. Emerging multicomponent electrocatalysts, integrating the advantages of individual components of catalysts, are of great importance to achieve efficient electroreduction of small molecules <em>via</em> activation of inert bonds and multistep transformation. In this review, some basic issues in the electroreduction of small molecules including CO<small>₂</small>, N<small>₂</small>, and NO<small>₃</small><small>⁻</small> are briefly introduced. We then discuss our fundamental understanding of the rule of interaction in multicomponent electrocatalysts, and summarize three models for multicomponent catalysts, including type I, “a non-catalytically active component can activate or protect another catalytic component”; type II, “all catalytic components provide active intermediates for electrochemical conversion”; and type III, “one component provides the substrate for the other through conversion or adsorption”. Additionally, an outlook was considered to highlight the future directions of multicomponent electrocatalysts toward industrial applications.</p><p>Keywords: Green chemistry; Green carbon science; Electrocatalysis; Synergetic effect.</p>","PeriodicalId":29808,"journal":{"name":"Industrial Chemistry & Materials","volume":" 1","pages":" 93-105"},"PeriodicalIF":0.0,"publicationDate":"2023-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/im/d2im00056c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49994633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Understanding the charging of supercapacitors by electrochemical quartz crystal microbalance","authors":"Liang Niu, Long Yang, Jingjing Yang, Ming Chen, Liang Zeng, Pan Duan, Taizheng Wu, Emmanuel Pameté, Volker Presser and Guang Feng","doi":"10.1039/D2IM00038E","DOIUrl":"https://doi.org/10.1039/D2IM00038E","url":null,"abstract":"<p>Supercapacitors are highly valued energy storage devices with high power density, fast charging ability, and exceptional cycling stability. A profound understanding of their charging mechanisms is crucial for continuous performance enhancement. Electrochemical quartz crystal microbalance (EQCM), a detection means that provides <em>in situ</em> mass change information during charging–discharging processes at the nanogram level, has received greatly significant attention during the past decade due to its high sensitivity, non-destructiveness and low cost. Since being used to track ionic fluxes in porous carbons in 2009, EQCM has played a pivotal role in understanding the charging mechanisms of supercapacitors. Herein, we review the critical progress of EQCM hitherto, including theory fundamentals and applications in supercapacitors. Finally, we discuss the fundamental effects of ion desolvation and transport on the performance of supercapacitors. The advantages and defects of applying EQCM in supercapacitors are thoroughly examined, and future directions are proposed.</p><p>Keywords: EQCM; Supercapacitors; Charging mechanisms; Quantitative characterization.</p>","PeriodicalId":29808,"journal":{"name":"Industrial Chemistry & Materials","volume":" 2","pages":" 175-187"},"PeriodicalIF":0.0,"publicationDate":"2022-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/im/d2im00038e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49994180","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hierarchically ordered porous carbon with atomically dispersed cobalt for oxidative esterification of furfural†","authors":"Wen Yao, Chenghong Hu, Yajie Zhang, Hao Li, Fengliang Wang, Kui Shen, Liyu Chen and Yingwei Li","doi":"10.1039/D2IM00045H","DOIUrl":"https://doi.org/10.1039/D2IM00045H","url":null,"abstract":"<p>Nitrogen-rich zeolitic imidazolate frameworks (ZIFs) are ideal precursors for the synthesis of metal single atoms anchored on N-doped carbon. However, the microporous structures of conventional ZIFs lead to low mass transfer efficiency and low metal utilization of their derivatives. Here, we construct a composite of Co single atoms anchored on nitrogen-doped carbon with a three-dimensional ordered macroporous structure (Co-SA/3DOM-NC) by two-step pyrolysis of ordered macro/microporous ZnCo-ZIF. Co-SA/3DOM-NC shows high activity in the oxidative esterification of furfural, achieving a 99% yield of methyl 2-furoate under mild reaction conditions, which is significantly superior to the microporous and the Co-nanoparticle counterparts. The high activity of Co-SA/3DOM-NC should be attributed to the CoN<small>₄</small> centers with high intrinsic activity and the ordered macroporous structure, promoting the mass transfer of reactants and accessibility of active sites.</p><p>Keywords: Heterogeneous catalysis; Hierarchical pores; Ordered macropore; Oxidative esterification reaction; Single-atom catalysts.</p>","PeriodicalId":29808,"journal":{"name":"Industrial Chemistry & Materials","volume":" 1","pages":" 106-116"},"PeriodicalIF":0.0,"publicationDate":"2022-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/im/d2im00045h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49995202","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Large-scale direct regeneration of LiFePO4@C based on spray drying†","authors":"Yongxing Zou, Jinwei Cao, Hao Li, Wanbao Wu, Yihong Liang and Jiaheng Zhang","doi":"10.1039/D2IM00007E","DOIUrl":"https://doi.org/10.1039/D2IM00007E","url":null,"abstract":"<p>Direct regeneration is a low-cost and environmentally friendly way of recycling spent Li-ion batteries. In this study, a new method is adopted to regenerate spent LiFePO<small>₄</small>. First, the spent LiFePO<small>₄</small> powder is homogenized, and then, small amounts of a lithium source and a carbon source are thoroughly mixed by spray drying. After that, a high-temperature solid-phase method is used to regenerate the carbon-coated lithium iron phosphate. Compared with traditional regeneration methods, the proposed method significantly improves the universality of spent LiFePO<small>₄</small> having different degrees of damage. The regenerated LiFePO<small>₄</small> is characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and electrochemical measurements. The results show that the regenerated sample has a stable morphology, structure, and electrochemical performance. Under the conditions of 0.1C, the initial capacity exceeds 160 mA h g<small>⁻¹</small>. After 800 cycles under the conditions of 1C, the capacity retention is 80%, which satisfies the requirements for regenerated LiFePO<small>₄</small> batteries.</p><p>Keywords: LiFePO<small>₄</small>; Direct regeneration; Homogenization; Spray drying; Electrochemical performance.</p>","PeriodicalId":29808,"journal":{"name":"Industrial Chemistry & Materials","volume":" 2","pages":" 254-261"},"PeriodicalIF":0.0,"publicationDate":"2022-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/im/d2im00007e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49994118","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Supercritical CO2-induced room-temperature ferromagnetism in two-dimensional MoO3−x†","authors":"Wei Liu and Qun Xu","doi":"10.1039/D2IM00028H","DOIUrl":"https://doi.org/10.1039/D2IM00028H","url":null,"abstract":"Two-dimensional (2D) magnetic semiconductors are crucial in spin-based information-processing technologies due to the combination of the strong 2D quantum, surface effects and the control of spin states. However, most experimental...","PeriodicalId":29808,"journal":{"name":"Industrial Chemistry & Materials","volume":" 1","pages":" 140-145"},"PeriodicalIF":0.0,"publicationDate":"2022-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/im/d2im00028h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49994178","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}