S. M. Abu Nayem, Aziz Ahmad, Syed Shaheen Shah, Atif Saeed Alzahrani, A. J. Saleh Ahammad, M. Aziz
{"title":"Cover Picture: High Performance and Long‐cycle Life Rechargeable Aluminum Ion Battery: Recent Progress, Perspectives and Challenges (Chem. Rec. 12/2022)","authors":"S. M. Abu Nayem, Aziz Ahmad, Syed Shaheen Shah, Atif Saeed Alzahrani, A. J. Saleh Ahammad, M. Aziz","doi":"10.1002/tcr.202281201","DOIUrl":"https://doi.org/10.1002/tcr.202281201","url":null,"abstract":"","PeriodicalId":22443,"journal":{"name":"The Chemical Record","volume":"28 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89488625","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organofluorine compounds have had an increasing impact in synthetic organic chemistry and pharmaceutical research over the past two decades. Their syntheses and the development of novel synthetic approaches towards versatile fluorinated small molecules have received great interest. Our research team has designed various selective and stereocontrolled methods for the construction of fluorine‐containing small molecular entities, involving the transformation of various functionalized cycloalkenes across their ring olefin bond. The synthetic methodologies developed to access various pharmacologically interesting fluorinated derivatives with multiple chiral centers might be valuable protocols for the preparation of other classes of organic compounds as well.
{"title":"Recent Progress in the Selective Fluorinations of Some Functionalized Cycloalkenes","authors":"Melinda Nonn, Csaba Paizs, L. Kiss","doi":"10.1002/tcr.202200130","DOIUrl":"https://doi.org/10.1002/tcr.202200130","url":null,"abstract":"Organofluorine compounds have had an increasing impact in synthetic organic chemistry and pharmaceutical research over the past two decades. Their syntheses and the development of novel synthetic approaches towards versatile fluorinated small molecules have received great interest. Our research team has designed various selective and stereocontrolled methods for the construction of fluorine‐containing small molecular entities, involving the transformation of various functionalized cycloalkenes across their ring olefin bond. The synthetic methodologies developed to access various pharmacologically interesting fluorinated derivatives with multiple chiral centers might be valuable protocols for the preparation of other classes of organic compounds as well.","PeriodicalId":22443,"journal":{"name":"The Chemical Record","volume":"16 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85940214","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Catalysts play a pivotal role in achieving the global need for food and energy. In this context, porous organic polymers (POPs) with high surface area, robust architecture, tunable pore size, and chemical functionalities have emerged as promising testbeds for heterogeneous catalysis. Amorphous POPs having functionalized interconnected hierarchical porous structures activate a diverse range of substrates through covalent/non‐covalent interactions or act as a host matrix to encapsulate catalytically active metal centers. On the other hand, conjugated POPs have been explored for photoinduced chemical transformations. In this personal account, we have delineated the evolution of various POPs and the specific role of pores and pore functionalities in heterogeneous catalysis. Subsequently, we retrospect our journey over the last ten years towards designing and fabricating amorphous POPs for heterogeneous catalysis, specifically photocatalytic reactive oxygen species (ROS)‐mediated organic transformations and nonredox chemical fixation of CO2. We have also outlined some of the future avenues of POPs and POP‐based hybrid materials for diverse catalytic applications.
{"title":"Porous Organic Polymers: Promising Testbed for Heterogeneous Reactive Oxygen Species Mediated Photocatalysis and Nonredox CO2 Fixation","authors":"Arkaprabha Giri, Abhijit Patra","doi":"10.1002/tcr.202200071","DOIUrl":"https://doi.org/10.1002/tcr.202200071","url":null,"abstract":"Catalysts play a pivotal role in achieving the global need for food and energy. In this context, porous organic polymers (POPs) with high surface area, robust architecture, tunable pore size, and chemical functionalities have emerged as promising testbeds for heterogeneous catalysis. Amorphous POPs having functionalized interconnected hierarchical porous structures activate a diverse range of substrates through covalent/non‐covalent interactions or act as a host matrix to encapsulate catalytically active metal centers. On the other hand, conjugated POPs have been explored for photoinduced chemical transformations. In this personal account, we have delineated the evolution of various POPs and the specific role of pores and pore functionalities in heterogeneous catalysis. Subsequently, we retrospect our journey over the last ten years towards designing and fabricating amorphous POPs for heterogeneous catalysis, specifically photocatalytic reactive oxygen species (ROS)‐mediated organic transformations and nonredox chemical fixation of CO2. We have also outlined some of the future avenues of POPs and POP‐based hybrid materials for diverse catalytic applications.","PeriodicalId":22443,"journal":{"name":"The Chemical Record","volume":"20 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79012707","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
R. Majee, Sahanaz Parvin, Quazi Arif Islam, Ashwani Kumar, Bharati Debnath, Surajit Mondal, Subhajit Bhattacharjee, Satarupa Das, Arun Kumar, S. Bhattacharyya
Modern day electrochemical devices find applications in a wide range of industrial sectors, from consumer electronics, renewable energy management to pollution control by electric vehicles and reduction of greenhouse gas. There has been a surge of diverse electrochemical systems which are to be scaled up from the lab‐scale to industry sectors. To achieve the targets, the electrocatalysts are continuously upgraded to meet the required device efficiency at a low cost, increased lifetime and performance. An atomic scale understanding is however important for meeting the objectives. Transitioning from the bulk to the nanoscale regime of the electrocatalysts, the existence of defects and interfaces is almost inevitable, significantly impacting (augmenting) the material properties and the catalytic performance. The intrinsic defects alter the electronic structure of the nanostructured catalysts, thereby boosting the performance of metal‐ion batteries, metal‐air batteries, supercapacitors, fuel cells, water electrolyzers etc. This account presents our findings on the methods to introduce measured imperfections in the nanomaterials and the impact of these atomic‐scale irregularities on the activity for three major reactions, oxygen evolution reaction (OER), oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). Grain boundary (GB) modulation of the (ABO3)n type perovskite oxide by noble metal doping is a propitious route to enhance the OER/ORR bifunctionality for zinc‐air battery (ZAB). The perovskite oxides can be tuned by calcination at different temperatures to alter the oxygen vacancy, GB fraction and overall reactivity. The oxygen defects, unsaturated coordination environment and GBs can turn a relatively less active nanostructure into an efficient redox active catalyst by imbibing plenty of electrochemically active sites. Obviously, the crystalline GB interface is a prerequisite for effective electron flow, which is also applicable for the crystalline surface oxide shell on metal alloy core of the nanoparticles (NPs). The oxygen vacancy of two‐dimensional (2D) perovskite oxide can be made reversible by the A‐site termination of the nanosheets, facilitating the reversible entry and exit of a secondary phase during the redox processes. In several instances, the secondary phases have been observed to introduce the right proportion of structural defects and orbital occupancies for adsorption and desorption of reaction intermediates. Also, heterogeneous interfaces can be created by wrapping the perovskite oxide with negatively charged surface by layered double hydroxide (LDH) can promote the OER process. In another approach, ion intercalation at the 2D heterointerfaces steers the interlayer spacing that can influence the mass diffusion. Similar to anion vacancy, controlled formation of the cation vacancies can be achieved by exsolving the B‐site cations of perovskite oxides to surface anchored catalytically active metal/alloy NPs. In cas
{"title":"The Perfect Imperfections in Electrocatalysts","authors":"R. Majee, Sahanaz Parvin, Quazi Arif Islam, Ashwani Kumar, Bharati Debnath, Surajit Mondal, Subhajit Bhattacharjee, Satarupa Das, Arun Kumar, S. Bhattacharyya","doi":"10.1002/tcr.202200070","DOIUrl":"https://doi.org/10.1002/tcr.202200070","url":null,"abstract":"Modern day electrochemical devices find applications in a wide range of industrial sectors, from consumer electronics, renewable energy management to pollution control by electric vehicles and reduction of greenhouse gas. There has been a surge of diverse electrochemical systems which are to be scaled up from the lab‐scale to industry sectors. To achieve the targets, the electrocatalysts are continuously upgraded to meet the required device efficiency at a low cost, increased lifetime and performance. An atomic scale understanding is however important for meeting the objectives. Transitioning from the bulk to the nanoscale regime of the electrocatalysts, the existence of defects and interfaces is almost inevitable, significantly impacting (augmenting) the material properties and the catalytic performance. The intrinsic defects alter the electronic structure of the nanostructured catalysts, thereby boosting the performance of metal‐ion batteries, metal‐air batteries, supercapacitors, fuel cells, water electrolyzers etc. This account presents our findings on the methods to introduce measured imperfections in the nanomaterials and the impact of these atomic‐scale irregularities on the activity for three major reactions, oxygen evolution reaction (OER), oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). Grain boundary (GB) modulation of the (ABO3)n type perovskite oxide by noble metal doping is a propitious route to enhance the OER/ORR bifunctionality for zinc‐air battery (ZAB). The perovskite oxides can be tuned by calcination at different temperatures to alter the oxygen vacancy, GB fraction and overall reactivity. The oxygen defects, unsaturated coordination environment and GBs can turn a relatively less active nanostructure into an efficient redox active catalyst by imbibing plenty of electrochemically active sites. Obviously, the crystalline GB interface is a prerequisite for effective electron flow, which is also applicable for the crystalline surface oxide shell on metal alloy core of the nanoparticles (NPs). The oxygen vacancy of two‐dimensional (2D) perovskite oxide can be made reversible by the A‐site termination of the nanosheets, facilitating the reversible entry and exit of a secondary phase during the redox processes. In several instances, the secondary phases have been observed to introduce the right proportion of structural defects and orbital occupancies for adsorption and desorption of reaction intermediates. Also, heterogeneous interfaces can be created by wrapping the perovskite oxide with negatively charged surface by layered double hydroxide (LDH) can promote the OER process. In another approach, ion intercalation at the 2D heterointerfaces steers the interlayer spacing that can influence the mass diffusion. Similar to anion vacancy, controlled formation of the cation vacancies can be achieved by exsolving the B‐site cations of perovskite oxides to surface anchored catalytically active metal/alloy NPs. In cas","PeriodicalId":22443,"journal":{"name":"The Chemical Record","volume":"15 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89908775","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
It is a reasonable question to ask, why, as of 1965 when the five Woodward‐Hoffmann communications appeared, did no other organic chemist discover the orbital symmetry rules for pericyclic reactions? Two theoretical chemists – Luitzen Oosterhoff (in 1961) and Kenichi Fukui (in 1964) had discovered portions of the orbital symmetry rules before Woodward and Hoffmann. Why not organic chemists? Indeed, perhaps the greatest motivation to discover the mechanism of a mysterious reaction is to uncover key examples of that mysterious reaction in your very own laboratory. The stories of 20 chemists and R. B. Woodward are discussed in this paper which is Paper 6 in a 27‐paper series on the history of Woodward‐Hoffmann rules. Social, political, and scientific explanations will also be presented as partial explanations as to why none of these individuals – except Woodward with Hoffmann – solved the pericyclic no‐mechanism problem.
{"title":"The Many Chemists Who Could Have Proposed the Woodward‐Hoffmann Rules But Didn't: The Organic Chemists Who Discovered the Smoking Guns[] **","authors":"J. I. Seeman","doi":"10.1002/tcr.202200065","DOIUrl":"https://doi.org/10.1002/tcr.202200065","url":null,"abstract":"It is a reasonable question to ask, why, as of 1965 when the five Woodward‐Hoffmann communications appeared, did no other organic chemist discover the orbital symmetry rules for pericyclic reactions? Two theoretical chemists – Luitzen Oosterhoff (in 1961) and Kenichi Fukui (in 1964) had discovered portions of the orbital symmetry rules before Woodward and Hoffmann. Why not organic chemists? Indeed, perhaps the greatest motivation to discover the mechanism of a mysterious reaction is to uncover key examples of that mysterious reaction in your very own laboratory. The stories of 20 chemists and R. B. Woodward are discussed in this paper which is Paper 6 in a 27‐paper series on the history of Woodward‐Hoffmann rules. Social, political, and scientific explanations will also be presented as partial explanations as to why none of these individuals – except Woodward with Hoffmann – solved the pericyclic no‐mechanism problem.","PeriodicalId":22443,"journal":{"name":"The Chemical Record","volume":"96 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84669990","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cobalt carbonates and derivatives represent most promising cost‐effective materials for energy storage, conversion and upgrading. Morphology determines the performances, as size, shape and electronic configuration are key factors for tunable properties in the area of batteries, catalysis, magnetics and plasmonics. However, there is lack of insights in literature on morphological control of cobalt carbonates during hydrothermal and solvothermal conditions. Therefore, this review provides detailed discussion on synthesis, formation mechanism and morphological control of nanosheets, wires, spheres and cubes of cobalt carbonates. Furthermore, the influence of experimental conditions and plausible mechanism which govern the growing processes were further discussed in details. The outcome of this short review will offer insights into rational design of inexpensive metal carbonates for numerous other energy and environment applications.
{"title":"Recent Advances on Synthesis of CoCO3 with Controlled Morphologies","authors":"Quanxing Zhang, Wei Yu, Dongpei Zhang, Mengyuan Liu, Jinyao Wang, Kexin Meng, Chaohe Yang, Xin Jin, Guangyu Zhang","doi":"10.1002/tcr.202200021","DOIUrl":"https://doi.org/10.1002/tcr.202200021","url":null,"abstract":"Cobalt carbonates and derivatives represent most promising cost‐effective materials for energy storage, conversion and upgrading. Morphology determines the performances, as size, shape and electronic configuration are key factors for tunable properties in the area of batteries, catalysis, magnetics and plasmonics. However, there is lack of insights in literature on morphological control of cobalt carbonates during hydrothermal and solvothermal conditions. Therefore, this review provides detailed discussion on synthesis, formation mechanism and morphological control of nanosheets, wires, spheres and cubes of cobalt carbonates. Furthermore, the influence of experimental conditions and plausible mechanism which govern the growing processes were further discussed in details. The outcome of this short review will offer insights into rational design of inexpensive metal carbonates for numerous other energy and environment applications.","PeriodicalId":22443,"journal":{"name":"The Chemical Record","volume":"19 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77215053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Transition metal dichalcogenides (TMDCs) have good flexibility, light absorption, and carrier mobility, and can be used to fabricate wearable devices and photodetectors. In addition, the band gaps of these materials are adjustable, which are related to the number of stacking layers. The the material properties can be changed by vertically stacking TMDCs to form van der Waals (vdW) heterostructures. Compared with single‐layer TMDC, the vdW heterostructure has better light response and more efficient photoelectric conversion. Interlayer excitons formed in vdW heterostructure have a longer exciton lifetime and unique valley selectivity compared with intralayer excitons, which promotes the research on TMDCs materials in photoelectric field, valley electronics, carrier dynamics, etc. In this paper, the methods of synthesizing heterostructures are introduced. Photoelectric properties, valley dynamics, electronic properties and related applications of TMDCs vdW heterostructures are also discussed. Heterostructures stacked with different materials, stacking modes, and twist angles all can affect the properties. Hence, it brings more creativity and research direction to the material field.
{"title":"Transition Metal Dichalcogenides (TMDCs) Heterostructures: Synthesis, Excitons and Photoelectric Properties","authors":"Jianuo Fan, Mengtao Sun","doi":"10.1002/tcr.202100313","DOIUrl":"https://doi.org/10.1002/tcr.202100313","url":null,"abstract":"Transition metal dichalcogenides (TMDCs) have good flexibility, light absorption, and carrier mobility, and can be used to fabricate wearable devices and photodetectors. In addition, the band gaps of these materials are adjustable, which are related to the number of stacking layers. The the material properties can be changed by vertically stacking TMDCs to form van der Waals (vdW) heterostructures. Compared with single‐layer TMDC, the vdW heterostructure has better light response and more efficient photoelectric conversion. Interlayer excitons formed in vdW heterostructure have a longer exciton lifetime and unique valley selectivity compared with intralayer excitons, which promotes the research on TMDCs materials in photoelectric field, valley electronics, carrier dynamics, etc. In this paper, the methods of synthesizing heterostructures are introduced. Photoelectric properties, valley dynamics, electronic properties and related applications of TMDCs vdW heterostructures are also discussed. Heterostructures stacked with different materials, stacking modes, and twist angles all can affect the properties. Hence, it brings more creativity and research direction to the material field.","PeriodicalId":22443,"journal":{"name":"The Chemical Record","volume":"37 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90881668","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Despite the recent advances in reconstructive orthopedics; fracture union is a challenge to bone regeneration. Concurrent angiogenesis is a complex process governed by events, delicately entwined with osteogenesis. However, poorly perfused scaffolds have lower success rates; necessitating the need for a better vascular component, which is important for the delivery of nutrients, oxygen, waste elimination, recruitment of cells for optimal bone repair. This review highlights the latest strategies to promote biomaterial‐based scaffold vascularization by incorporation of cells, growth factors, inorganic ions, etc. into natural or synthetic polymers, ceramic materials, or composites of organic and inorganic compounds. Furthermore, it emphasizes structural modifications, biophysical stimuli, and natural molecules to fabricate scaffolds aiding the genesis of dense vascularization following their implantation to manifest a compatible regenerative microenvironment without graft rejection.
{"title":"Strategies for Enhancing Vascularization of Biomaterial‐Based Scaffold in Bone Regeneration","authors":"Jasna Nambiar, S. Jana, S. Nandi","doi":"10.1002/tcr.202200008","DOIUrl":"https://doi.org/10.1002/tcr.202200008","url":null,"abstract":"Despite the recent advances in reconstructive orthopedics; fracture union is a challenge to bone regeneration. Concurrent angiogenesis is a complex process governed by events, delicately entwined with osteogenesis. However, poorly perfused scaffolds have lower success rates; necessitating the need for a better vascular component, which is important for the delivery of nutrients, oxygen, waste elimination, recruitment of cells for optimal bone repair. This review highlights the latest strategies to promote biomaterial‐based scaffold vascularization by incorporation of cells, growth factors, inorganic ions, etc. into natural or synthetic polymers, ceramic materials, or composites of organic and inorganic compounds. Furthermore, it emphasizes structural modifications, biophysical stimuli, and natural molecules to fabricate scaffolds aiding the genesis of dense vascularization following their implantation to manifest a compatible regenerative microenvironment without graft rejection.","PeriodicalId":22443,"journal":{"name":"The Chemical Record","volume":"44 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83639594","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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