Pub Date : 2024-09-05DOI: 10.1038/s44160-024-00622-5
Le Shi, Yuanlong Zhong, Honghao Cao, Hao Wang, Zhangyi Xiong, Kun Wang, Hanyang Shen, Zhijie Chen
Supermolecular building block (SBB) approaches have been widely used for synthesizing highly connected metal–organic frameworks (MOFs). However, it remains a challenge to synthesize trinodal MOFs via SBB approaches. Here we report the assembly of (3,12,24)-connected uru-MOFs via a hetero-supermolecular-building-block (hetero-SBB) strategy, that is, using different types of highly connected metal–organic polyhedra (MOPs) as building units. This hetero-SBB strategy allows the facile synthesis of previously inaccessible uru-MOFs via 12-connected cuboctahedral and 24-connected rhombicuboctahedral MOPs. The uru-MOF-1, consisting of hierarchical microporous and mesoporous cages, exhibits a Brunauer–Emmett–Teller area of 3,170 m2 g−1. This MOF shows a high methane uptake of 339.6 cm3 (standard temperature and pressure) cm−3 at 159 K and 10 bar and is a promising candidate for low-temperature methane storage. The hetero-SBB strategy paves a way for the designed synthesis of highly connected MOFs, which are difficult to synthesize via traditional strategies, by taking advantage of the arsenal of synthetic MOPs.
{"title":"A hetero-supermolecular-building-block strategy for the assembly of porous (3,12,24)-connected uru metal–organic frameworks","authors":"Le Shi, Yuanlong Zhong, Honghao Cao, Hao Wang, Zhangyi Xiong, Kun Wang, Hanyang Shen, Zhijie Chen","doi":"10.1038/s44160-024-00622-5","DOIUrl":"https://doi.org/10.1038/s44160-024-00622-5","url":null,"abstract":"<p>Supermolecular building block (SBB) approaches have been widely used for synthesizing highly connected metal–organic frameworks (MOFs). However, it remains a challenge to synthesize trinodal MOFs via SBB approaches. Here we report the assembly of (3,12,24)-connected uru-MOFs via a hetero-supermolecular-building-block (hetero-SBB) strategy, that is, using different types of highly connected metal–organic polyhedra (MOPs) as building units. This hetero-SBB strategy allows the facile synthesis of previously inaccessible uru-MOFs via 12-connected cuboctahedral and 24-connected rhombicuboctahedral MOPs. The uru-MOF-1, consisting of hierarchical microporous and mesoporous cages, exhibits a Brunauer–Emmett–Teller area of 3,170 m<sup>2</sup> g<sup>−1</sup>. This MOF shows a high methane uptake of 339.6 cm<sup>3</sup> (standard temperature and pressure) cm<sup>−3</sup> at 159 K and 10 bar and is a promising candidate for low-temperature methane storage. The hetero-SBB strategy paves a way for the designed synthesis of highly connected MOFs, which are difficult to synthesize via traditional strategies, by taking advantage of the arsenal of synthetic MOPs.</p><figure></figure>","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195623","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}
Pub Date : 2024-09-05DOI: 10.1038/s44160-024-00638-x
Jiyeon Kim, Dongsik Nam, Hye Jin Cho, Eunchan Cho, Dharmalingam Sivanesan, Changhyeon Cho, Jaewoong Lee, Jihan Kim, Wonyoung Choe
The vast structural diversity of metal–organic frameworks (MOFs) and the ability to tailor the structures makes the materials applicable for a broad range of uses. Traditional bottom-up and top-down design approaches have enabled a rapid increase in this structural diversity, yet the systematic screening for unknown synthesizable MOFs remains a challenge. Here we report a design strategy, the up–down approach, by merging the bottom-up and top-down approaches. This approach bridges the advantages of both methods, creating a synergistic strategy for discovering MOF structures. Targeting Zr-based MOFs, we search promising topology candidates and unveiled 26 future structural configurations by considering the possible orientations of Zr6 clusters. Through ribbon representation and sophisticated analysis of the ligand angles, we suggest structure models and synthesize Zr6-based MOFs with bct (1) and scu (1) configurations. The up–down approach will accelerate the discovery of previously unknown or inaccessible MOFs, providing exciting opportunities to expand the chemical space of MOFs.
{"title":"Up–down approach for expanding the chemical space of metal–organic frameworks","authors":"Jiyeon Kim, Dongsik Nam, Hye Jin Cho, Eunchan Cho, Dharmalingam Sivanesan, Changhyeon Cho, Jaewoong Lee, Jihan Kim, Wonyoung Choe","doi":"10.1038/s44160-024-00638-x","DOIUrl":"https://doi.org/10.1038/s44160-024-00638-x","url":null,"abstract":"<p>The vast structural diversity of metal–organic frameworks (MOFs) and the ability to tailor the structures makes the materials applicable for a broad range of uses. Traditional bottom-up and top-down design approaches have enabled a rapid increase in this structural diversity, yet the systematic screening for unknown synthesizable MOFs remains a challenge. Here we report a design strategy, the up–down approach, by merging the bottom-up and top-down approaches. This approach bridges the advantages of both methods, creating a synergistic strategy for discovering MOF structures. Targeting Zr-based MOFs, we search promising topology candidates and unveiled 26 future structural configurations by considering the possible orientations of Zr<sub>6</sub> clusters. Through ribbon representation and sophisticated analysis of the ligand angles, we suggest structure models and synthesize Zr<sub>6</sub>-based MOFs with <b>bct (1)</b> and <b>scu (1)</b> configurations. The up–down approach will accelerate the discovery of previously unknown or inaccessible MOFs, providing exciting opportunities to expand the chemical space of MOFs.</p><figure></figure>","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195628","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}
Pub Date : 2024-09-02DOI: 10.1038/s44160-024-00642-1
William B. Martin, Robert E. Warburton, Shane M. Parker, Valentin O. Rodionov
{"title":"On the characterization of γ-graphyne","authors":"William B. Martin, Robert E. Warburton, Shane M. Parker, Valentin O. Rodionov","doi":"10.1038/s44160-024-00642-1","DOIUrl":"10.1038/s44160-024-00642-1","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195625","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}
Pub Date : 2024-08-30DOI: 10.1038/s44160-024-00641-2
A strategy is demonstrated for the hierarchical assembly of highly crystalline supramolecular nanotubes and tubular covalent organic frameworks (COFs), driven by cooperative dynamic covalent and coordination bonding. The pore size of the tubular COFs can be precisely controlled, and their reversible demetallation and remetallation could enable further tuning of the properties.
{"title":"Integrating multiple interactions for the assembly of ordered organic frameworks","authors":"","doi":"10.1038/s44160-024-00641-2","DOIUrl":"https://doi.org/10.1038/s44160-024-00641-2","url":null,"abstract":"A strategy is demonstrated for the hierarchical assembly of highly crystalline supramolecular nanotubes and tubular covalent organic frameworks (COFs), driven by cooperative dynamic covalent and coordination bonding. The pore size of the tubular COFs can be precisely controlled, and their reversible demetallation and remetallation could enable further tuning of the properties.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195627","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}
Pub Date : 2024-08-30DOI: 10.1038/s44160-024-00651-0
Alexandra R. Groves
{"title":"Methane to methanol","authors":"Alexandra R. Groves","doi":"10.1038/s44160-024-00651-0","DOIUrl":"10.1038/s44160-024-00651-0","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142170384","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}
Pub Date : 2024-08-28DOI: 10.1038/s44160-024-00621-6
Tae-Ung Wi, Yongchao Xie, Zachary H. Levell, Danyi Feng, Jung Yoon ‘Timothy’ Kim, Peng Zhu, Ahmad Elgazzar, Tae Hwa Jeon, Mohsen Shakouri, Shaoyun Hao, Zhiwei Fang, Chang Qiu, Hyun-Wook Lee, Andrea Hicks, Yuanyue Liu, Chong Liu, Haotian Wang
It is challenging to obtain high-value hydrocarbons that are longer than C3 via electrochemical CO2/CO reduction. Integrating electrochemical CO2/CO electrolysers with a downstream bioreactor is one solution for obtaining high-value long-chain products, but the electrolytes in these two systems are mismatched, preventing smooth integration. Here we demonstrate a porous solid electrolyte reactor that produces highly selective and electrolyte-free acetate and couple it with a biosynthesis system for generating C4+ polyhydroxybutyrate bioplastic. A finely tuned electrolyte containing biocompatible salt medium with acetate can be directly injected into the downstream bioreactor without any separation or salt-mixing processes. In the optimized coupled platform, Ralstonia eutropha bacteria can grow with acetate generated from the CO electrocatalytic reduction reactor, and produce bioplastic as the final value-added product. Integrating electrochemical CO electrolysers with a bioreactor can yield high-value long-chain carbon products, but the electrolytes for the two systems are mismatched. Now, a porous solid electrolyte reactor, which can produce acetate directly in bioelectrolyte, is demonstrated. Direct integration with a bioreactor produces bioplastic from CO via the acetate intermediate.
{"title":"Upgrading carbon monoxide to bioplastics via integrated electrochemical reduction and biosynthesis","authors":"Tae-Ung Wi, Yongchao Xie, Zachary H. Levell, Danyi Feng, Jung Yoon ‘Timothy’ Kim, Peng Zhu, Ahmad Elgazzar, Tae Hwa Jeon, Mohsen Shakouri, Shaoyun Hao, Zhiwei Fang, Chang Qiu, Hyun-Wook Lee, Andrea Hicks, Yuanyue Liu, Chong Liu, Haotian Wang","doi":"10.1038/s44160-024-00621-6","DOIUrl":"10.1038/s44160-024-00621-6","url":null,"abstract":"It is challenging to obtain high-value hydrocarbons that are longer than C3 via electrochemical CO2/CO reduction. Integrating electrochemical CO2/CO electrolysers with a downstream bioreactor is one solution for obtaining high-value long-chain products, but the electrolytes in these two systems are mismatched, preventing smooth integration. Here we demonstrate a porous solid electrolyte reactor that produces highly selective and electrolyte-free acetate and couple it with a biosynthesis system for generating C4+ polyhydroxybutyrate bioplastic. A finely tuned electrolyte containing biocompatible salt medium with acetate can be directly injected into the downstream bioreactor without any separation or salt-mixing processes. In the optimized coupled platform, Ralstonia eutropha bacteria can grow with acetate generated from the CO electrocatalytic reduction reactor, and produce bioplastic as the final value-added product. Integrating electrochemical CO electrolysers with a bioreactor can yield high-value long-chain carbon products, but the electrolytes for the two systems are mismatched. Now, a porous solid electrolyte reactor, which can produce acetate directly in bioelectrolyte, is demonstrated. Direct integration with a bioreactor produces bioplastic from CO via the acetate intermediate.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195629","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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