Pub Date : 2025-01-09DOI: 10.1016/j.chempr.2024.08.021
Jordan L.S. Zackasee , Valmuri Srivardhan , Blaise L. Truesdell , Elizabeth J. Vrana , Christo S. Sevov
Polyvinyl chloride (PVC) plastics require high loadings of plasticizers and stabilizers to achieve commercially useful bulk properties. However, these non-covalent additives leach from PVC over time, resulting in the loss of their tailored functionality. This work details the electrocatalytic functionalization of PVC to covalently graft plasticizing additives directly onto the polymer backbone. Here, mechanistic insights guided the design of electrocatalysts capable of modifying C–Cl bonds of PVC under mild conditions with high selectivity while suppressing side reactions such as elimination and chain scission. Functional groups that mimic PVC plasticizers are covalently installed into the backbone of PVC to create new materials with distinct bulk properties from the original polymer. The degree of polymer grafting is easily controlled by simply changing the redox capacity that is passed during electrolysis. This strategy is employed to create chemically and leach-resistant PVC materials by directly electrolyzing mixtures of consumer PVC products.
{"title":"Electrocatalytic grafting of polyvinyl chloride plastics","authors":"Jordan L.S. Zackasee , Valmuri Srivardhan , Blaise L. Truesdell , Elizabeth J. Vrana , Christo S. Sevov","doi":"10.1016/j.chempr.2024.08.021","DOIUrl":"10.1016/j.chempr.2024.08.021","url":null,"abstract":"<div><div>Polyvinyl chloride (PVC) plastics require high loadings of plasticizers and stabilizers to achieve commercially useful bulk properties. However, these non-covalent additives leach from PVC over time, resulting in the loss of their tailored functionality. This work details the electrocatalytic functionalization of PVC to covalently graft plasticizing additives directly onto the polymer backbone. Here, mechanistic insights guided the design of electrocatalysts capable of modifying C–Cl bonds of PVC under mild conditions with high selectivity while suppressing side reactions such as elimination and chain scission. Functional groups that mimic PVC plasticizers are covalently installed into the backbone of PVC to create new materials with distinct bulk properties from the original polymer. The degree of polymer grafting is easily controlled by simply changing the redox capacity that is passed during electrolysis. This strategy is employed to create chemically and leach-resistant PVC materials by directly electrolyzing mixtures of consumer PVC products.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102298"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142246239","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}
Pub Date : 2025-01-09DOI: 10.1016/j.chempr.2024.10.012
Weidong Dai , Kaiwei Wan , Kanglei Pang , Jun Guo , Siyuan Liu , Keying Wu , Chiyao Tang , Yanjuan Sun , Xinghua Shi , Zhiyong Tang , Chang Long , Fan Dong
Renewable energy-driven heterogeneous electrocatalysis holds tremendous potential in converting earth-abundant small molecules and industrial pollutants into value-added or environmentally friendly chemicals, sparking global research interest. The catalyst-electrolyte interface has long been at the forefront of heterogeneous electrocatalysis, dealing with the structure-performance relationship between the performance and the catalytic system, consisting of catalysts, electrolytes, and external biases, at the molecular or atomic level. However, recent observations of numerous surface reconstruction phenomena have challenged the traditional research paradigm that relies on static interface models to elucidate structure-performance relationships. This perspective focuses on the catalyst-electrolyte interface model and rationalizes the underlying principles of catalyst surface reconstruction behavior in terms of free energy. It then showcases the influence of pre-catalyst structure, electrolyte (including additives and reaction intermediates), and external bias on surface reconstruction, alongside state-of-the-art modulation strategies based on the current understanding of surface construction. Finally, we highlight critical issues for future research on catalyst surface reconstruction, including the unexplored factors influencing reconstruction and reaction types, the necessary developments in in situ characterization and simulation techniques, and the currently overlooked problem of catalyst deactivation.
{"title":"In-depth understanding and precise modulation of surface reconstruction during heterogeneous electrocatalysis: From model to practical catalyst","authors":"Weidong Dai , Kaiwei Wan , Kanglei Pang , Jun Guo , Siyuan Liu , Keying Wu , Chiyao Tang , Yanjuan Sun , Xinghua Shi , Zhiyong Tang , Chang Long , Fan Dong","doi":"10.1016/j.chempr.2024.10.012","DOIUrl":"10.1016/j.chempr.2024.10.012","url":null,"abstract":"<div><div>Renewable energy-driven heterogeneous electrocatalysis holds tremendous potential in converting earth-abundant small molecules and industrial pollutants into value-added or environmentally friendly chemicals, sparking global research interest. The catalyst-electrolyte interface has long been at the forefront of heterogeneous electrocatalysis, dealing with the structure-performance relationship between the performance and the catalytic system, consisting of catalysts, electrolytes, and external biases, at the molecular or atomic level. However, recent observations of numerous surface reconstruction phenomena have challenged the traditional research paradigm that relies on static interface models to elucidate structure-performance relationships. This perspective focuses on the catalyst-electrolyte interface model and rationalizes the underlying principles of catalyst surface reconstruction behavior in terms of free energy. It then showcases the influence of pre-catalyst structure, electrolyte (including additives and reaction intermediates), and external bias on surface reconstruction, alongside state-of-the-art modulation strategies based on the current understanding of surface construction. Finally, we highlight critical issues for future research on catalyst surface reconstruction, including the unexplored factors influencing reconstruction and reaction types, the necessary developments in <em>in situ</em> characterization and simulation techniques, and the currently overlooked problem of catalyst deactivation.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102345"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937582","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}
Pub Date : 2025-01-09DOI: 10.1016/j.chempr.2024.08.011
Yuchong Yang , Tanya K. Ronson , Paula C.P. Teeuwen , Yuyin Du , Jieyu Zheng , David J. Wales , Jonathan R. Nitschke
Inspired by natural systems, metal-organic cages with well-defined shapes and cavities can be tuned for different guest-binding functions. Here, we report the construction of two types of cage frameworks: an MII12L8 (M = ZnII and CoII) pseudo-cuboctahedral architecture 1 and a rarer MII9L8 (M = ZnII and CoII) pseudo-Johnson-solid-type (J51) framework 2. Both structures form from the same boron-containing triamine subcomponent, and each one incorporates hexacoordinate metal vertices chelated by only two bidentate pyridyl(imine) arms. Such vertices provide the cages with the flexibility required to form lower-symmetry architectures, and they also facilitate reversible disassembly in response to fluoride. These cages were also shown to respond to other chemical stimuli enabling transformation between cage structures. Cage 1 bound different guest molecules, including the anticancer drug paclitaxel, C-methylcalix[4]resorcinarene, and tetraphenylborates. The release of paclitaxel by 1 was stimulated by fluoride or chloride, highlighting the potential for applications in natural product separation and drug delivery.
{"title":"Guest binding is governed by multiple stimuli in low-symmetry metal-organic cages containing bis-pyridyl(imine) vertices","authors":"Yuchong Yang , Tanya K. Ronson , Paula C.P. Teeuwen , Yuyin Du , Jieyu Zheng , David J. Wales , Jonathan R. Nitschke","doi":"10.1016/j.chempr.2024.08.011","DOIUrl":"10.1016/j.chempr.2024.08.011","url":null,"abstract":"<div><div>Inspired by natural systems, metal-organic cages with well-defined shapes and cavities can be tuned for different guest-binding functions. Here, we report the construction of two types of cage frameworks: an M<sup>II</sup><sub>12</sub>L<sub>8</sub> (M = Zn<sup>II</sup> and Co<sup>II</sup>) <em>pseudo</em>-cuboctahedral architecture <strong>1</strong> and a rarer M<sup>II</sup><sub>9</sub>L<sub>8</sub> (M = Zn<sup>II</sup> and Co<sup>II</sup>) <em>pseudo</em>-Johnson-solid-type (<em>J</em><sub>51</sub>) framework <strong>2</strong>. Both structures form from the same boron-containing triamine subcomponent, and each one incorporates hexacoordinate metal vertices chelated by only two bidentate pyridyl(imine) arms. Such vertices provide the cages with the flexibility required to form lower-symmetry architectures, and they also facilitate reversible disassembly in response to fluoride. These cages were also shown to respond to other chemical stimuli enabling transformation between cage structures. Cage <strong>1</strong> bound different guest molecules, including the anticancer drug paclitaxel, <em>C</em>-methylcalix[4]resorcinarene, and tetraphenylborates. The release of paclitaxel by <strong>1</strong> was stimulated by fluoride or chloride, highlighting the potential for applications in natural product separation and drug delivery.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102288"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142221774","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}
Pub Date : 2025-01-09DOI: 10.1016/j.chempr.2024.09.004
Jun Xu , Yuting Yang , Huanyu Jin , Yao Zheng , Shi-Zhang Qiao
Rationally designing anode electrocatalysts is crucial for advancing next-generation proton exchange membrane water electrolyzers (PEMWEs). However, the most developed oxygen evolution catalysts in labs often cannot be directly applied to commercial PEMWEs due to differences in durability, performance, and cost. In this perspective, we review these gaps between fundamental lab research and practical device requirements and propose solutions to bridge them. We cover degradation mechanisms and durability evaluations in lab-scale aqueous model systems (AMSs) and PEMWEs. The need for performance benchmarking for anode screening and assessment is addressed, emphasizing reliable test protocols in AMSs and PEMWEs. Additionally, we discuss the importance of cost reduction in anodic catalyst design for future PEMWEs systems. Finally, we highlight major challenges and propose outlooks for anode design in fab-oriented applications to achieve the ultimate green hydrogen goal of “1 kg H2 produced by 1 USD in 1 decade” (“111” goal).
{"title":"Bridging gaps between lab- and fab-oriented anode design for proton exchange membrane water electrolyzers","authors":"Jun Xu , Yuting Yang , Huanyu Jin , Yao Zheng , Shi-Zhang Qiao","doi":"10.1016/j.chempr.2024.09.004","DOIUrl":"10.1016/j.chempr.2024.09.004","url":null,"abstract":"<div><div>Rationally designing anode electrocatalysts is crucial for advancing next-generation proton exchange membrane water electrolyzers (PEMWEs). However, the most developed oxygen evolution catalysts in labs often cannot be directly applied to commercial PEMWEs due to differences in durability, performance, and cost. In this perspective, we review these gaps between fundamental lab research and practical device requirements and propose solutions to bridge them. We cover degradation mechanisms and durability evaluations in lab-scale aqueous model systems (AMSs) and PEMWEs. The need for performance benchmarking for anode screening and assessment is addressed, emphasizing reliable test protocols in AMSs and PEMWEs. Additionally, we discuss the importance of cost reduction in anodic catalyst design for future PEMWEs systems. Finally, we highlight major challenges and propose outlooks for anode design in fab-oriented applications to achieve the ultimate green hydrogen goal of “1 kg H<sub>2</sub> produced by 1 USD in 1 decade” (“111” goal).</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102305"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398237","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}
Pub Date : 2025-01-09DOI: 10.1016/j.chempr.2024.07.035
Jian-Xin Wang , Osama Shekhah , Osman M. Bakr , Mohamed Eddaoudi , Omar F. Mohammed
X-ray imaging scintillators are essential for numerous technologies that impact our daily lives, including medical radiography, computed tomography, and security inspection. Organic materials have emerged as potential alternatives for X-ray imaging scintillators due to their low toxicity, high stability, and large-area fabrication. However, their low X-ray absorption cross-section and inefficient exciton utilization efficiency limit their practical applications and commercialization. Nevertheless, these drawbacks can be mitigated through efficient energy transfer from suitable X-ray sensitizers. In this review, we summarize recent progress in fabricating high-performance energy transfer-based scintillators using a variety of X-ray sensitizers and emission centers and provide a detailed interpretation of the corresponding energy transfer mechanisms and their tremendous impact on the operation of X-ray imaging scintillators. Furthermore, we have also carefully considered the impact of various factors within the imaging system, including the X-ray source, light-matter interaction, and photodetector, on the overall imaging performance.
X 射线成像闪烁体对于影响我们日常生活的众多技术来说至关重要，其中包括医疗射线照相术、计算机断层扫描和安全检查。有机材料因其低毒性、高稳定性和大面积制造而成为 X 射线成像闪烁体的潜在替代品。然而，有机材料对 X 射线的吸收截面小、激子利用效率低，限制了其实际应用和商业化。不过，这些缺点可以通过合适的 X 射线敏化剂进行有效的能量转移来缓解。在本综述中，我们总结了利用各种 X 射线敏化剂和发射中心制造基于能量转移的高性能闪烁体的最新进展，并详细解释了相应的能量转移机制及其对 X 射线成像闪烁体工作的巨大影响。此外，我们还仔细考虑了成像系统中各种因素（包括 X 射线源、光物质相互作用和光电探测器）对整体成像性能的影响。
{"title":"Energy transfer-based X-ray imaging scintillators","authors":"Jian-Xin Wang , Osama Shekhah , Osman M. Bakr , Mohamed Eddaoudi , Omar F. Mohammed","doi":"10.1016/j.chempr.2024.07.035","DOIUrl":"10.1016/j.chempr.2024.07.035","url":null,"abstract":"<div><div>X-ray imaging scintillators are essential for numerous technologies that impact our daily lives, including medical radiography, computed tomography, and security inspection. Organic materials have emerged as potential alternatives for X-ray imaging scintillators due to their low toxicity, high stability, and large-area fabrication. However, their low X-ray absorption cross-section and inefficient exciton utilization efficiency limit their practical applications and commercialization. Nevertheless, these drawbacks can be mitigated through efficient energy transfer from suitable X-ray sensitizers. In this review, we summarize recent progress in fabricating high-performance energy transfer-based scintillators using a variety of X-ray sensitizers and emission centers and provide a detailed interpretation of the corresponding energy transfer mechanisms and their tremendous impact on the operation of X-ray imaging scintillators. Furthermore, we have also carefully considered the impact of various factors within the imaging system, including the X-ray source, light-matter interaction, and photodetector, on the overall imaging performance.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102273"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142138189","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}
Pub Date : 2025-01-09DOI: 10.1016/j.chempr.2024.09.002
Manjur O. Akram , Caleb D. Martin
In this issue of Chem, Kinjo and Feng report the synthesis of a cyclotriborate trianion (B3R63−), a highly charged boron ring system with discrete two-center two-electron bonds. With three contiguous borates, the B33− core of the feature compound defies Coulomb’s law and represents the first homocyclic boron analog of the ubiquitous cyclopropane. The remarkable stability enabled full characterization and opens new vistas in the field of multiply charged boron ions.
{"title":"The cyclotriborate trianion","authors":"Manjur O. Akram , Caleb D. Martin","doi":"10.1016/j.chempr.2024.09.002","DOIUrl":"10.1016/j.chempr.2024.09.002","url":null,"abstract":"<div><div>In this issue of <em>Chem</em>, Kinjo and Feng report the synthesis of a cyclotriborate trianion (B<sub>3</sub>R<sub>6</sub><sup>3−</sup>), a highly charged boron ring system with discrete two-center two-electron bonds. With three contiguous borates, the B<sub>3</sub><sup>3−</sup> core of the feature compound defies Coulomb’s law and represents the first homocyclic boron analog of the ubiquitous cyclopropane. The remarkable stability enabled full characterization and opens new vistas in the field of multiply charged boron ions.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102303"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142439926","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}
Pub Date : 2025-01-08DOI: 10.1016/j.chempr.2024.11.017
Ananya Mishra, Avinash J. Patil, Stephen Mann
The construction of biomimetic agents capable of generating precise outcomes in response to specific molecular inputs is a central challenge for the development of programmable synthetic cells with integrated biomimetic functions. Here, we harness acoustic standing waves to generate periodic microarrays of enzyme-encoded coacervate microdroplets for the implementation of embodied enzyme logic circuits (EELCs). We describe a range of biocatalytic communication channels capable of performing localized and distributed Boolean logic functions in single or segregated populations of model protocells by using a range of molecular inputs, fluorescence or hydrogelation outputs, and programmable response dynamics. To implement long-range collective signal processing, we integrate EELC modules across spatially segregated protocell populations to generate distributed time-regulated logic operations involving negative feedback, pulse generation, and redirected output-input connectivity. Our results provide a step toward the non-DNA programming of model protocell communication and computational networks for miniaturized autonomous sensing devices capable of chemical-based information processing.
{"title":"Biocatalytic programming of protocell-embodied logic gates and circuits","authors":"Ananya Mishra, Avinash J. Patil, Stephen Mann","doi":"10.1016/j.chempr.2024.11.017","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.017","url":null,"abstract":"The construction of biomimetic agents capable of generating precise outcomes in response to specific molecular inputs is a central challenge for the development of programmable synthetic cells with integrated biomimetic functions. Here, we harness acoustic standing waves to generate periodic microarrays of enzyme-encoded coacervate microdroplets for the implementation of embodied enzyme logic circuits (EELCs). We describe a range of biocatalytic communication channels capable of performing localized and distributed Boolean logic functions in single or segregated populations of model protocells by using a range of molecular inputs, fluorescence or hydrogelation outputs, and programmable response dynamics. To implement long-range collective signal processing, we integrate EELC modules across spatially segregated protocell populations to generate distributed time-regulated logic operations involving negative feedback, pulse generation, and redirected output-input connectivity. Our results provide a step toward the non-DNA programming of model protocell communication and computational networks for miniaturized autonomous sensing devices capable of chemical-based information processing.","PeriodicalId":268,"journal":{"name":"Chem","volume":"56 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936132","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}
Pub Date : 2025-01-06DOI: 10.1016/j.chempr.2024.12.003
Elwy H. Abdelkader, Haocheng Qianzhu, Gottfried Otting, Thomas Huber
Few chemistries are suitable for in-cell protein labeling, and the required reagents are costly. We present an approach for the coupled biosynthesis and genetic encoding of activated nitriles, delivering a facile way to furnish proteins with biocompatible reactive handles suitable for subsequent site-specific modifications both in cell and in vitro. The strategy utilizes the endogenous bacterial cysteine biosynthetic machinery to produce the nitrile-bearing non-canonical amino acids (ncAAs) in situ and then perform genetic encoding through an engineered orthogonal translation system. We demonstrate the utility of our system for rapid site-specific bioconjugation and macrocyclization through the nitrile-aminothiol (NAT) click reaction. In addition, we introduce the aromatic condensation NAT (arcNAT) click reaction as a tool for generating a diverse array of turn-on fluorophores. arcNAT achieves fluorogenic labeling of proteins for live-cell microscopy without requiring washing steps. Our approach provides a uniquely convenient, versatile, and cost-effective platform for the post-translational diversification of proteins.
{"title":"Biosynthesis and genetic encoding of activated nitriles for fast protein conjugation and tunable fluorogenic labeling","authors":"Elwy H. Abdelkader, Haocheng Qianzhu, Gottfried Otting, Thomas Huber","doi":"10.1016/j.chempr.2024.12.003","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.12.003","url":null,"abstract":"Few chemistries are suitable for in-cell protein labeling, and the required reagents are costly. We present an approach for the coupled biosynthesis and genetic encoding of activated nitriles, delivering a facile way to furnish proteins with biocompatible reactive handles suitable for subsequent site-specific modifications both in cell and <em>in vitro</em>. The strategy utilizes the endogenous bacterial cysteine biosynthetic machinery to produce the nitrile-bearing non-canonical amino acids (ncAAs) <em>in situ</em> and then perform genetic encoding through an engineered orthogonal translation system. We demonstrate the utility of our system for rapid site-specific bioconjugation and macrocyclization through the nitrile-aminothiol (NAT) click reaction. In addition, we introduce the aromatic condensation NAT (arcNAT) click reaction as a tool for generating a diverse array of turn-on fluorophores. arcNAT achieves fluorogenic labeling of proteins for live-cell microscopy without requiring washing steps. Our approach provides a uniquely convenient, versatile, and cost-effective platform for the post-translational diversification of proteins.","PeriodicalId":268,"journal":{"name":"Chem","volume":"4 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929625","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}
Pub Date : 2025-01-03DOI: 10.1016/j.chempr.2024.11.019
Na Chen, Jing Xi, Tianpei He, Ruichen Shen, Rui Zhao, Haoming Chi, Jia Yao, Na Du, Lilei Yu, Yun Zhang, Tianyou Peng, Tiangang Liu, Quan Yuan
Inspired by the solar energy storage process during photosynthesis, we report herein a solar-decoupled photosynthetic biohybrid strategy through integrating a persistent photocatalyst with photoautotrophic microbes for sustainable and all-weather biomanufacturing, allowing for overcoming the intrinsic intermittent nature of solar energy availability by introducing energy storage and release processes. The results demonstrate that the apparent photo conversion efficiency (APCE) for of the persistent catalyst/R. palustris hybrid system reaches 8.30%, much higher than the 4.36% observed in bare R. palustris. Additionally, the proposed solar-decoupled biohybrid strategy not only shows considerable potential in coupling the practical power plant for the capture and utilization of CO2 from the flue gas but also exhibits universal applicability in different photosynthetic microorganisms. This concept-proving research offers new ideas to extend photocatalysis reactions without in situ irradiation and could pave new ways for sustainable solar energy utilization as well as biomanufacturing in space, where solar energy might be limited.
{"title":"Beyond natural synthesis via solar-decoupled biohybrid photosynthetic system","authors":"Na Chen, Jing Xi, Tianpei He, Ruichen Shen, Rui Zhao, Haoming Chi, Jia Yao, Na Du, Lilei Yu, Yun Zhang, Tianyou Peng, Tiangang Liu, Quan Yuan","doi":"10.1016/j.chempr.2024.11.019","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.019","url":null,"abstract":"Inspired by the solar energy storage process during photosynthesis, we report herein a solar-decoupled photosynthetic biohybrid strategy through integrating a persistent photocatalyst with photoautotrophic microbes for sustainable and all-weather biomanufacturing, allowing for overcoming the intrinsic intermittent nature of solar energy availability by introducing energy storage and release processes. The results demonstrate that the apparent photo conversion efficiency (APCE) for of the persistent catalyst/<em>R</em>. <em>palustris</em> hybrid system reaches 8.30%, much higher than the 4.36% observed in bare <em>R. palustris</em>. Additionally, the proposed solar-decoupled biohybrid strategy not only shows considerable potential in coupling the practical power plant for the capture and utilization of CO<sub>2</sub> from the flue gas but also exhibits universal applicability in different photosynthetic microorganisms. This concept-proving research offers new ideas to extend photocatalysis reactions without <em>in situ</em> irradiation and could pave new ways for sustainable solar energy utilization as well as biomanufacturing in space, where solar energy might be limited.","PeriodicalId":268,"journal":{"name":"Chem","volume":"32 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917917","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}
Dispersing the catalytically more active noble metal at the single-site scale ensures maximum atom efficiency for selective heterogeneous hydrogenation over bimetallic particles. However, the low density and random location of the noble-metal atoms compromise the intrinsic activity and/or selectivity because of the resulting altered electronic structure. Here, we report that densely populating and precisely arranging Pt atoms in the form of a Pt-Fe-Pt heterotrimer not only catalyzes preferential hydrogenation of the C=O bond in crotonaldehyde (CAL) but also increases the reaction rate by 35-fold, circumventing the activity-selectivity trade-off. The Pt-Fe-Pt active site is fabricated by H2 reduction at 673 K of a Pt-Fe2O3 particle pair, wherein a 3.3 nm Pt particle sits on a 9.8 nm Fe2O3 particle. It interacts with the CAL molecule in a site-bond recognition manner: the left-end Pt atom anchors the C=C bond, whereas the central Fe atom activates the C=O bond, which is further hydrogenated by H atoms adsorbed on the right-end Pt atom.
将催化活性更高的贵金属分散在单位点尺度上，可确保在双金属颗粒上进行选择性非均相氢化的最大原子效率。然而，由于贵金属原子的低密度和随机位置，导致电子结构改变，从而损害了其固有活性和/或选择性。在这里，我们报道了密集填充和精确排列Pt原子以Pt- fe -Pt异质三聚体的形式不仅催化巴丁醛（CAL）中C=O键的优先氢化，而且还将反应速率提高了35倍，绕过了活性-选择性权衡。在673 K下H2还原Pt-Fe2O3粒子对制备了Pt- fe -Pt活性位点，其中3.3 nm的Pt粒子位于9.8 nm的Fe2O3粒子上。它以位点键识别的方式与CAL分子相互作用：左端Pt原子锚定C=C键，而中心Fe原子激活C=O键，C=O键被吸附在右端Pt原子上的H原子进一步氢化。
{"title":"Fine-tuned coordination environment of Pt-Fe-Pt active site for selective heterogeneous hydrogenation of crotonaldehyde","authors":"Di Zhou, Junjun Wang, Minzhen Jian, Yong Li, Zheng Jiang, Shuang Liu, Yan Zhou, Jiake Wei, Christof Wöll, Wei-Xue Li, Yuemin Wang, Wenjie Shen","doi":"10.1016/j.chempr.2024.11.018","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.018","url":null,"abstract":"Dispersing the catalytically more active noble metal at the single-site scale ensures maximum atom efficiency for selective heterogeneous hydrogenation over bimetallic particles. However, the low density and random location of the noble-metal atoms compromise the intrinsic activity and/or selectivity because of the resulting altered electronic structure. Here, we report that densely populating and precisely arranging Pt atoms in the form of a Pt-Fe-Pt heterotrimer not only catalyzes preferential hydrogenation of the C=O bond in crotonaldehyde (CAL) but also increases the reaction rate by 35-fold, circumventing the activity-selectivity trade-off. The Pt-Fe-Pt active site is fabricated by H<sub>2</sub> reduction at 673 K of a Pt-Fe<sub>2</sub>O<sub>3</sub> particle pair, wherein a 3.3 nm Pt particle sits on a 9.8 nm Fe<sub>2</sub>O<sub>3</sub> particle. It interacts with the CAL molecule in a site-bond recognition manner: the left-end Pt atom anchors the C=C bond, whereas the central Fe atom activates the C=O bond, which is further hydrogenated by H atoms adsorbed on the right-end Pt atom.","PeriodicalId":268,"journal":{"name":"Chem","volume":"75 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917848","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}
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