National Science Review最新文献_第9页

Ru3@Mo2CO2 MXene single-cluster catalyst for highly efficient N2-to-NH3 conversion 用于实现 N2 到 NH3 高效转化的 Ru3@Mo2CO2 MXene 单簇催化剂

IF 20.6 1区综合性期刊

National Science Review Pub Date : 2024-07-25 DOI: 10.1093/nsr/nwae251

Cong Zhang, Ze-Hui Wang, Haiyan Wang, Jin-Xia Liang, Chun Zhu, Jun Li

{"title":"Ru3@Mo2CO2 MXene single-cluster catalyst for highly efficient N2-to-NH3 conversion","authors":"Cong Zhang, Ze-Hui Wang, Haiyan Wang, Jin-Xia Liang, Chun Zhu, Jun Li","doi":"10.1093/nsr/nwae251","DOIUrl":"https://doi.org/10.1093/nsr/nwae251","url":null,"abstract":"Single-cluster catalysts (SCCs) representing structurally well-defined metal clusters anchored on support tend to exhibit tuneable catalytic performance for complex redox reactions in heterogeneous catalysis. Here we report a theoretical study on an SCC of Ru3@Mo2CO2 MXene for N2-to-NH3 thermal conversion. Our results show that Ru3@Mo2CO2 can effectively activate N2 and promotes its conversion to NH3 through an association mechanism, in which the rate-determining step of NH2* + H* → NH3* has a low energy barrier of 1.29 eV. Especially, with the assistance of Mo2CO2 support, the positively charged Ru3 cluster active site can effectively adsorb and activate N2, leading to 0.74 |e| charge transfer from Ru3@Mo2CO2 to the adsorbed N2. The supported Ru3 also acts as an electron reservoir to regulate the charge transfer for various intermediate steps of ammonia synthesis. Microkinetic analysis shows that the turnover frequency (TOF) of the N2-to-NH3 conversion on Ru3@Mo2CO2 is as high as 1.45 × 10−2 s−1 site−1 at a selected thermodynamic condition of 48 bar and 700 K, the performance of which even surpasses those of the Ru B5 site and Fe3/θ-Al2O3(010) reported before. Our work provides a theoretical understanding on the high stability and catalytic mechanism of Ru3@Mo2CO2 and guidance for further designing and fabricating MXene-based metal SCCs for ammonia synthesis under mild conditions.","PeriodicalId":18842,"journal":{"name":"National Science Review","volume":"8 1","pages":""},"PeriodicalIF":20.6,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141770100","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Electronic perturbation of Cu nanowire surfaces with functionalized graphdiyne for enhanced CO2 reduction reaction 用功能化石墨二炔对铜纳米线表面进行电子扰动以增强二氧化碳还原反应

IF 20.6 1区综合性期刊

National Science Review Pub Date : 2024-07-25 DOI: 10.1093/nsr/nwae253

Haiyuan Zou, Dongfang Cheng, Chao Tang, Wen Luo, Huatian Xiong, Hongliang Dong, Fan Li, Tao Song, Siyan Shu, Hao Dai, Ziang Cui, Zhouguang Lu, Lele Duan

{"title":"Electronic perturbation of Cu nanowire surfaces with functionalized graphdiyne for enhanced CO2 reduction reaction","authors":"Haiyuan Zou, Dongfang Cheng, Chao Tang, Wen Luo, Huatian Xiong, Hongliang Dong, Fan Li, Tao Song, Siyan Shu, Hao Dai, Ziang Cui, Zhouguang Lu, Lele Duan","doi":"10.1093/nsr/nwae253","DOIUrl":"https://doi.org/10.1093/nsr/nwae253","url":null,"abstract":"Electronic perturbation of Cu catalysts surface is crucial for optimizing electrochemical CO2 reduction activity, yet still poses great challenges. Herein, nanostructured Cu nanowires (NW) with fine-tuned surface electronic structure are achieved via surface encapsulation with electron-withdrawing (–F) and -donating (–Me) group-functionalized graphdiynes (R-GDY, R = –F and –Me), and the resulting catalysts, denoted as R-GDY/Cu NW, display distinct CO2 reduction performances. In-situ electrochemical spectroscopy revealed that the *CO (a key intermediate of the CO2 reduction reaction) binding affinity and consequent *CO coverage positively correlate to the Cu surface oxidation state, leading to the favorable C–C coupling on F-GDY/Cu NW over Me-GDY/Cu NW. Electrochemical measurements corroborate the favorable C2H4 production with an optimum C2+ selectivity of 73.15% ± 2.5% observed for F-GDY/Cu NW, while the predominant CH4 production is favored by Me-GDY/Cu NW. Furthermore, leveraging the *Cu–OH/*CO ratio as a descriptor, mechanistic investigation reveals that the protonation of distinct adsorbed *CO facilitated by *Cu–OH is crucial for the selective generation of C2H4 and CH4 on F-GDY/Cu NW and Me-GDY/Cu NW, respectively.","PeriodicalId":18842,"journal":{"name":"National Science Review","volume":"142 1","pages":""},"PeriodicalIF":20.6,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141770104","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

IF 20.6 1区综合性期刊

National Science Review Pub Date : 2024-07-25 DOI: 10.1093/nsr/nwae257

Wei Li, Rizheng He, Xiaohui Yuan, Felix Schneider, Frederik Tilmann, Zhen Guo, Yongshun John Chen

引用次数: 0

Construction of chiral crown ethers into robust covalent organic frameworks for electrochromatographic enantioseparation 将手性冠醚构建成用于电色谱对映体分离的坚固共价有机框架

IF 20.6 1区综合性期刊

National Science Review Pub Date : 2024-07-25 DOI: 10.1093/nsr/nwae256

Shiguo Fu, Gaizhao Qin, Jinqiao Dong, Chen Yuan, Yan Liu, Li-Ming Yuan, Yong Cui

{"title":"Construction of chiral crown ethers into robust covalent organic frameworks for electrochromatographic enantioseparation","authors":"Shiguo Fu, Gaizhao Qin, Jinqiao Dong, Chen Yuan, Yan Liu, Li-Ming Yuan, Yong Cui","doi":"10.1093/nsr/nwae256","DOIUrl":"https://doi.org/10.1093/nsr/nwae256","url":null,"abstract":"Capillary electrochromatography (CEC) is a rapidly emerging separation technique that merges the high separation efficiency of capillary electrophoresis with the exceptional selectivity of liquid chromatography. However, it remains a synthetic challenge to design functional chiral stationary phases (CSPs) with high chemical stability against acid and base in CEC enantioseparation. Here we demonstrate that incorporating chiral crown ethers into stable covalent organic frameworks (COFs) enable efficient and stable separations of racemates by CEC. This facilitates us to craft two three-dimensional chiral COFs (CCOFs) by polycondensation of a chiral 1,1'-binaphyl-20-crown-6-derived dialdehyde and tetraamines with diisopropyl substituents. Both feature a 11-fold interpenetrated diamond framework, characterized by tubular open channels decorated with chiral crown ethers serving as enantioselective recognition and binding sites. These frameworks demonstrate excellent stability in water, acid, and base, thanks to the presence of bulky iso-propyl groups that shield the dynamic imine linkages. Moreover, the precisely defined COF channels enhanced the accessibility of the enclosed crown ethers to the analytes while providing strong protection against harsh environments, rendering them suitable for CSPs in CEC separations. They can effectively separate some important enantiomers, including ketones, epoxides, and alkaline substances, when utilized as coatings on chiral columns, particularly facilitating the chiral separation of drugs. This study advances the application of COFs in electrochromatographic separations, expanding the scope of porous materials design and engineering to create COFs with targeted enantioselective properties.","PeriodicalId":18842,"journal":{"name":"National Science Review","volume":"12 1","pages":""},"PeriodicalIF":20.6,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141770099","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Understanding the local environment in electrocatalysis 了解电催化过程中的局部环境

IF 20.6 1区综合性期刊

National Science Review Pub Date : 2024-07-25 DOI: 10.1093/nsr/nwae250

Chaojie Chen, Yao Zheng, Shi-Zhang Qiao

引用次数: 0

Journey to the east: the oldest tetrapod fauna of east Pangea in early Permian 东方之旅：二叠纪早期泛大陆东部最古老的四足动物群落

IF 20.6 1区综合性期刊

National Science Review Pub Date : 2024-07-22 DOI: 10.1093/nsr/nwae249

Jianye Chen, Jun Liu

引用次数: 0

Regulating interaction with surface ligands on Au25 nanoclusters by multivariate metal-organic framework hosts for boosting catalysis 通过多元金属有机框架宿主调节与 Au25 纳米团簇表面配体的相互作用以提高催化性能

IF 20.6 1区综合性期刊

National Science Review Pub Date : 2024-07-20 DOI: 10.1093/nsr/nwae252

He Wang, Xiaokang Liu, Yulong Zhao, Zhihu Sun, Yue Lin, Tao Yao, Hai-Long Jiang

{"title":"Regulating interaction with surface ligands on Au25 nanoclusters by multivariate metal-organic framework hosts for boosting catalysis","authors":"He Wang, Xiaokang Liu, Yulong Zhao, Zhihu Sun, Yue Lin, Tao Yao, Hai-Long Jiang","doi":"10.1093/nsr/nwae252","DOIUrl":"https://doi.org/10.1093/nsr/nwae252","url":null,"abstract":"While atomically precise metal nanoclusters (NCs) with unique structures and reactivity are very promising in catalysis, the spatial resistance caused by the surface ligands and structural instability significantly poses great challenges. In this work, Au25(Cys)18 NCs are encapsulated in multivariate metal-organic frameworks (MOFs) to afford Au25@M-MOF-74 (M = Zn, Ni, Co, Mg). By the MOF confinement, the Au25 NCs showcase much enhanced activity and stability in the intramolecular cascade reaction of 2-nitrobenzonitrile. Notably, the interaction between the metal nodes in M-MOF-74 and Au25(Cys)18 is able to suppress the free vibration of the surface ligands on the Au25 NCs and thereby improve the accessibility of Au sites; meanwhile, the stronger interactions lead to higher electron density and core expansion within Au25(Cys)18. As a result, the activity exhibits the trend of Au25@Ni-MOF-74 &gt; Au25@Co-MOF-74 &gt; Au25@Zn-MOF-74 &gt; Au25@Mg-MOF-74, highlighting the crucial roles of microenvironment modulation around the Au25 NCs by interaction between the surface ligands and MOF hosts.","PeriodicalId":18842,"journal":{"name":"National Science Review","volume":"124 1","pages":""},"PeriodicalIF":20.6,"publicationDate":"2024-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141770106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Biomimetic Materials Research, from Interest-driven to Society-serving: An interview with Shu-Hong Yu 仿生材料研究，从利益驱动到服务社会：专访于淑红

IF 20.6 1区综合性期刊

National Science Review Pub Date : 2024-07-18 DOI: 10.1093/nsr/nwae246

Weijie Zhao

引用次数: 0

Investigating thermal properties of 2D non-layered material using a NEMS-based 2-DOF approach towards ultrahigh-performance bolometer 利用基于 NEMS 的 2-DOF 方法研究二维非分层材料的热特性，实现超高性能螺栓计

IF 20.6 1区综合性期刊

National Science Review Pub Date : 2024-07-18 DOI: 10.1093/nsr/nwae248

Luming Wang, Song Wu, Zejuan Zhang, Jiankai Zhu, Luwei Zou, Bo Xu, Jiaqi Wu, Junzhi Zhu, Fei Xiao, Chenyin Jiao, Shenghai Pei, Jiaze Qin, Yu Zhou, Juan Xia, Zenghui Wang

{"title":"Investigating thermal properties of 2D non-layered material using a NEMS-based 2-DOF approach towards ultrahigh-performance bolometer","authors":"Luming Wang, Song Wu, Zejuan Zhang, Jiankai Zhu, Luwei Zou, Bo Xu, Jiaqi Wu, Junzhi Zhu, Fei Xiao, Chenyin Jiao, Shenghai Pei, Jiaze Qin, Yu Zhou, Juan Xia, Zenghui Wang","doi":"10.1093/nsr/nwae248","DOIUrl":"https://doi.org/10.1093/nsr/nwae248","url":null,"abstract":"Two-dimensional (2D) non-layered materials in many aspects differ from their layered counterparts, and the exploration of their physical properties has produced many intriguing findings. However, due to challenges in applying existing experimental techniques to such nanoscale samples, their thermal properties have remained largely uncharacterized, hindering further exploration and device applications using this promising material system. Here, we demonstrate an experimental study of thermal conduction in β-In2S3, a typical non-layered 2D material, using a resonant nanoelectromechanical systems (NEMS) platform. We devise a new two-degrees-of-freedom technique, more responsive and sensitive than Raman spectroscopy, to simultaneously determine both the thermal conductivity to be 3.7 Wm−1K−1 and its interfacial thermal conductance with SiO2 as 6.4 MWm−2K−1. Leveraging such unique thermal properties, we further demonstrate a record-high power-to-frequency responsivity of −447 ppm/μW in β-In2S3 NEMS sensors, the best among drumhead NEMS-based bolometers. Our findings offer an effective approach for studying thermal properties and exploring potential thermal applications of 2D non-layered materials.","PeriodicalId":18842,"journal":{"name":"National Science Review","volume":"21 1","pages":""},"PeriodicalIF":20.6,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141737138","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Spin-related excited-state phenomena in photochemistry 光化学中与自旋有关的激发态现象

IF 20.6 1区综合性期刊

National Science Review Pub Date : 2024-07-17 DOI: 10.1093/nsr/nwae244

Chuang Zhang, Chen Ye, Jiannian Yao, Li-Zhu Wu

引用次数: 0