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2. Atom Transfer Radical Addition of Activated Primary Alkyl Chlorides Using In Situ Generated [Cp*RuII(Cl)(PR3)] Catalysts.
- Author
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van Leeuwen, Nicole S., Mathew, Simon, van Lare, Coert E. J., Ahr, Mathieu P., Zwijnenburg, Aalbert, Pullen, Sonja, and de Bruin, Bas
- Subjects
- *
ALKYL chlorides , *RADICALS (Chemistry) , *DENSITY functional theory , *ATOMS , *REDUCTION potential - Abstract
Atom transfer radical addition (ATRA) of halogenated compounds with alkenes is well established but primary alkyl chlorides are understudied because of the difficult C−Cl bond activation. In this paper, we show that TONs of 61 can be achieved in the ATRA of ethyl chloroacetate onto styrene with [Cp*Ru(Cl)2(PPh3)] and 1,1′‐azobis(cyclohexanecarbonitrile) (ACHN) as a radical initiator, representing a three‐fold improvement compared to previous reports. New catalyst precursors of the type [Cp*Ru(Cl)2(PR3)] were synthesized and tested (R=Me, Et, Cy, Ph, p‐CF3C6H4 and p‐MeOC6H4). The kinetic reaction profiles were studied using in situ ATR−FTIR spectroscopy. Among these complexes, [Cp*Ru(Cl)2(PPh3)] gave the best yields while [Cp*Ru(Cl)2(PMe3)] showed the highest rate. While rates correlate with redox potentials (electronics), our investigation reveals that substrate sterics are important for the overall yield. Density functional theory calculations suggest an open‐shell singlet pathway, where polymerization is kinetically disfavored, explaining the selectivity towards ATRA products. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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3. Atom Mediated Single‐Photon Nonlinearity in a Quadratically Coupled Optomechanical System.
- Author
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Liu, Q. H., Wang, G. C., Luan, T. Z., and Shen, H. Z.
- Subjects
MODE-coupling theory (Phase transformations) ,QUANTUM optics ,COUPLINGS (Gearing) ,POWER transmission ,ATOMS ,STATISTICAL correlation - Abstract
In this paper, conventional phonon blockade (CPNB) and conventional photon blockade (CPTB) effects, as well as unconventional phonon blockade (UPB) effects, are studied in an optomechanical system with nonlinear interaction between the cavity frequency and the square of the mechanical displacement driven by an external field, where a two‐level atom couples with the mechanical mode and a microwave driving field pumps cavity mode. The second‐order correlation function is analytically calculated, which is in good agreement with the numerical simulation given by the master equation. With energy‐level diagram, the atom‐mechanical mode coupling is found to induces the degeneracy splitting of the states and give the optimal conditions for CPNB and CPTB in this system. With the origin of UPB, the optimal conditions are derived and it is found that the realization of UPB is determined by the two couplings of the cavity and atom with respect to the mechanical mode. Moreover, some discussions on the experimental implementation in this quadratically coupled optomechanical system are presented. This study provides a possible way for realizing single‐photon nonlinearity and can extend the applications of optomechanical systems in the field of quantum optics. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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4. Progresses and Prospects of Asymmetrically Coordinated Single Atom Catalysts for Lithium−Sulfur Batteries.
- Author
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Zhou, Rong, Gu, Shaonan, Guo, Meng, Xu, Shuzheng, and Zhou, Guowei
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LITHIUM sulfur batteries ,CATALYSTS ,ATOMS ,CATALYTIC activity ,CATALYST structure - Abstract
Lithium–sulfur batteries (LSBs) are widely regarded as promising next‐generation batteries due to their high theoretical specific capacity and low material cost. However, the practical applications of LSBs are limited by the shuttle effect of lithium polysulfides (LiPSs), electronic insulation of charge and discharge products, and slow LiPSs conversion reaction kinetics. Accordingly, the introduction of catalysts into LSBs is one of the effective strategy to solve the issues of the sluggished LiPS conversion. Because of their nearly 100% atom utilization and high electrocatalytic activity, single‐atom catalysts (SACs) have been widely used as reaction mediators for LSBs' reactions. Excitingly, the SACs with asymmetric coordination structures have exhibited intriguing electronic structures and superior catalytic activities when compared to the traditional M–N4 active sites. In this review, we systematically describe the recent advancements in the installation of asymmetrically coordinated single‐atom structure as reactions catalysts in LSBs, including asymmetrically nitrogen coordinated SACs, heteroatom coordinated SACs, support effective asymmetrically coordinated SACs, and bimetallic coordinated SACs. Particularly noteworthy is the discussion of the catalytic conversion mechanism of LiPSs spanning asymmetrically coordinated SACs. Finally, a perspective on the future developments of asymmetrically coordinated SACs in LSB applications is provided. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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- View/download PDF
5. Coupling Ni Single Atomic Sites with Metallic Aggregates at Adjacent Geometry on Carbon Support for Efficient Hydrogen Peroxide Electrosynthesis.
- Author
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Wang, Xin, Huang, Run, Mao, Xin, Liu, Tian, Guo, Panjie, Sun, Hai, Mao, Zhelin, Han, Chao, Zheng, Yarong, Du, Aijun, Liu, Jianwei, Jia, Yi, and Wang, Lei
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ELECTROSYNTHESIS ,HYDROGEN peroxide ,GEOMETRY ,CARBON ,ATOMS ,NANOPARTICLES - Abstract
Single atomic catalysts have shown great potential in efficiently electro‐converting O2 to H2O2 with high selectivity. However, the impact of coordination environment and introduction of extra metallic aggregates on catalytic performance still remains unclear. Herein, first a series of carbon‐based catalysts with embedded coupling Ni single atomic sites and corresponding metallic nanoparticles at adjacent geometry is synthesized. Careful performance evaluation reveals NiSA/NiNP‐NSCNT catalyst with precisely controlled active centers of synergetic adjacent Ni‐N4S single sites and crystalline Ni nanoparticles exhibits a high H2O2 selectivity over 92.7% within a wide potential range (maximum selectivity can reach 98.4%). Theoretical studies uncover that spatially coupling single atomic NiN4S sites with metallic Ni aggregates in close proximity can optimize the adsorption behavior of key intermediates *OOH to achieve a nearly ideal binding strength, which thus affording a kinetically favorable pathway for H2O2 production. This strategy of manipulating the interaction between single atoms and metallic aggregates offers a promising direction to design new high‐performance catalysts for practical H2O2 electrosynthesis. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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6. CORRECTION.
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PHYSICS , *ATOMS - Abstract
This document is a correction to a previous article titled "Superionic State in Alumina Produced by Nonthermal Melting." The correction addresses a mistake in a script that resulted in incorrect absorbed doses calculated for different electronic temperatures. The corrected values are provided in Table 1. The authors state that all other results and conclusions of the original paper are unaffected. The document includes contact information for the authors and the DOI for the original article. [Extracted from the article]
- Published
- 2024
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7. Recent Progress of Electrochemical Nitrate Reduction to Ammonia on Copper‐Based Catalysts: From Nanoparticles to Single Atoms.
- Author
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Yu, Zixun, Gu, Mingyao, Wang, Yangyang, Li, Hao, Chen, Yuan, and Wei, Li
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DENITRIFICATION ,SUSTAINABILITY ,ELECTROLYTIC reduction ,HABER-Bosch process ,CATALYSTS ,ATOMS ,NANOPARTICLES ,AMMONIA - Abstract
Ammonia (NH3) is a vital chemical for modern human society. It is conventionally produced by the energy‐ and emission‐intensive Haber–Bosch process. Alternatively, sustainable NH3 production from renewable electricity‐driven electrolyzers has emerged as a promising route. Particularly, NH3 synthesis from nitrate (NO3−), a common pollutant in water and soil, by the nitrate reduction reaction (NO3RR) has drawn wide attention. Among various catalysts demonstrated recently, copper (Cu)‐based catalysts have been recognized as attractive candidates due to their availability, good activity, high NH3 selectivity, and facile reaction kinetics. In this review, the recent progress of Cu‐based NO3RR catalysts from the reaction mechanistic fundamentals to various catalyst design strategies, aiming at providing an on‐time summary, is summarized, and perspectives that can guide the rational and on‐demand design of Cu‐ and other earth‐abundant metal‐based catalysts for selective NO3RR toward sustainable NH3 production are elucidated. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
8. Nonconventional aggregation‐induced emission polysiloxanes: Structures, characteristics, and applications.
- Author
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Zhao, Yan, Xu, Lei, He, Yanyun, Feng, Zhixuan, Feng, Weixu, and Yan, Hongxia
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SILICONES ,LUMINOPHORES ,ELECTRON delocalization ,MOLECULAR structure ,ATOMS - Abstract
Nonconventional luminescent materials have been rising stars in organic luminophores due to their intrinsic characteristics, including water‐solubility, biocompatibility, and environmental friendliness and have shown potential applications in diverse fields. As an indispensable branch of nonconventional luminescent materials, polysiloxanes, which consist of electron‐rich auxochromic groups, have exhibited outstanding photophysical properties due to the unique silicon atoms. The flexible Si‐O bonds benefit the aggregation, and the empty 3d orbitals of Si atoms can generate coordination bonds including N → Si and O → Si, altering the electron delocalization of the material and improving the luminescent purity. Herein, we review the recent progress in luminescent polysiloxanes with different topologies and discuss the challenges and perspectives. With an emphasis on the driving force for the aggregation and the mechanism of tuned emissions, the role of Si atoms played in the nonconventional luminophores is highlighted. This review may provide new insights into the design of nonconventional luminescent materials and expand their further applications in sensing, biomedicine, lighting devices, etc. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
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9. Atomically Dispersed ZnN4 Sites Anchored on P‐Functionalized Carbon with Hierarchically Ordered Porous Structures for Boosted Electroreduction of CO2.
- Author
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Hu, Chenghong, Yao, Wen, Yang, Xianfeng, Shen, Kui, Chen, Liyu, and Li, Yingwei
- Subjects
STANDARD hydrogen electrode ,POROSITY ,ELECTRONIC structure ,CARBON ,ATOMS ,ELECTROLYTIC reduction ,MACROPOROUS polymers ,HYDROGEN evolution reactions - Abstract
Tuning the coordination structures of metal sites is intensively studied to improve the performances of single‐atom site catalysts (SASC). However, the pore structure of SASC, which is highly related to the accessibility of active sites, has received little attention. In this work, single‐atom ZnN4 sites embedded in P‐functionalized carbon with hollow‐wall and 3D ordered macroporous structure (denoted as H‐3DOM‐ZnN4/P‐C) are constructed. The creation of hollow walls in ordered macroporous structures can largely increase the external surface area to expose more active sites. The introduction of adjacent P atoms can optimize the electronic structure of ZnN4 sites through long‐rang regulation to enhance the intrinsic activity and selectivity. In the electrochemical CO2 reduction reaction, H‐3DOM‐ZnN4/P‐C exhibits high CO Faradaic efficiency over 90% in a wide potential window (500 mV) and a large turnover frequency up to 7.8 × 104 h−1 at −1.0 V versus reversible hydrogen electrode, much higher than its counterparts without the hierarchically ordered structure or P‐functionalization. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
10. High‐rate electrochemical H2O2 production over multimetallic atom catalysts under acidic–neutral conditions.
- Author
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Tong, Yueyu, Liu, Jiaxin, Su, Bing‐Jian, Juang, Jenh‐Yih, Hou, Feng, Yin, Lichang, Dou, Shi Xue, and Liang, Ji
- Subjects
OXYGEN reduction ,ELECTROLYTIC reduction ,ELECTRON configuration ,CATALYSTS ,ATOMS ,DENSITY functional theory ,HYDROGEN peroxide - Abstract
Hydrogen peroxide (H2O2) production by the electrochemical 2‐electron oxygen reduction reaction (2e− ORR) is a promising alternative to the energy‐intensive anthraquinone process, and single‐atom electrocatalysts show the unique capability of high selectivity toward 2e− ORR against the 4e− one. The extremely low surface density of the single‐atom sites and the inflexibility in manipulating their geometric/electronic configurations, however, compromise the H2O2 yield and impede further performance enhancement. Herein, we construct a family of multiatom catalysts (MACs), on which two or three single atoms are closely coordinated to form high‐density active sites that are versatile in their atomic configurations for optimal adsorption of essential *OOH species. Among them, the Cox–Ni MAC presents excellent electrocatalytic performance for 2e− ORR, in terms of its exceptionally high H2O2 yield in acidic electrolytes (28.96 mol L−1 gcat.−1 h−1) and high selectivity under acidic to neutral conditions in a wide potential region (>80%, 0–0.7 V). Operando X‐ray absorption and density functional theory analyses jointly unveil its unique trimetallic Co2NiN8 configuration, which efficiently induces an appropriate Ni–d orbital filling and modulates the *OOH adsorption, together boosting the electrocatalytic 2e− ORR capability. This work thus provides a new MAC strategy for tuning the geometric/electronic structure of active sites for 2e− ORR and other potential electrochemical processes. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
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