Sluggish reaction kinetics of oxygen evolution reaction(OER), resulting from multistep proton-coupled electron transfer and spin constriction, limits overall efficiency for most reported catalysts. Herein, using model...Sluggish reaction kinetics of oxygen evolution reaction(OER), resulting from multistep proton-coupled electron transfer and spin constriction, limits overall efficiency for most reported catalysts. Herein, using modeled ZnFe_(2-x)Ni_xO_(4)(0 ≤ x ≤ 0.4) spinel oxides, we aim to develop better OER electrocatalyst through combining the construction of ferromagnetic(FM) ordering channels and generation of highly active reconstructed species. The number of symmetry-breaking Fe–O–Ni structure links to the formation of FM ordering electron transfer channels. Meanwhile, as the number of Ni^(3+)increases, more ligand holes are formed, beneficial for redirecting surface reconstruction. The electro-activated ZnFe_(1.6)Ni_(0.4)O_(4) shows the highest specific activity, which is 13 and 2.5 times higher than that of ZnFe_(2)O_(4) and unactivated ZnFe_(1.6)Ni_(0.4)O_(4), and even superior to the benchmark IrO_(2) under the overpotential of 350 mV. Applying external magnetic field can make electron spin more aligned, and the activity can be further improved to 39 times of ZnFe_(2)O_(4). We propose that intriguing FM exchange-field interaction at FM/paramagnetic interfaces can penetrate FM ordering channels into reconstructed oxyhydroxide layers, thereby activating oxyhydroxide layers as spin-filter to accelerate spin-selective electron transfer. This work provides a new guideline to develop highly efficient spintronic catalysts for water oxidation and other spin-forbidden reactions.展开更多
The Antikythera mechanism is the most famous ancient astronomical calculator. The damaged excavation is a critical constraint for decoding the mechanism completely. By the systematic reconstruction design methodology,...The Antikythera mechanism is the most famous ancient astronomical calculator. The damaged excavation is a critical constraint for decoding the mechanism completely. By the systematic reconstruction design methodology, all feasible designs of the moon phase display device, which is one of the unclear mechanisms of the Antikythera mechanism, are reconstructed. These designs, including ordinary gear trains and epicyclic gear trains, are the simplest designs and satisfy the surviving evidence. The Antikythera mechanism and its reconstruction designs presented by LIN and YAN are introduced first. Three pointer types of the Antikythera mechanism are concluded based on their display motions and the orientation of the mechanism. In accordance with the analysis of the available interior reconstruction designs and the surviving evidence, four feasible designs of the moon phase display device are generated. All of them utilize the ball pointer with black and white that rotates around the radial axis to show cyclic moon phase. Two of these four feasible reconstruction designs are driven by one input source, and their bronze disks are fixed and rotatable respectively. Both of the remaining reconstruction designs are driven by two input sources, and their bronze disks are rotatable. Therefore, the four reconstruction designs of the moon phase display device reveal all possible display conditions of the moon phase pointers and the possible purposes of the bronze disk.展开更多
基金supported by the National Key R&D Program of China (2020YFA0710000)the National Natural Science Foundation of China (22278307, 22008170, 21978200, 22161142002, and 22121004)+2 种基金the Applied Basic Research Program of Qinghai Province (2023-ZJ-701)the Haihe Laboratory of Sustainable Chemical Transformationsthe Tianjin Research Innovation Project for Postgraduate Students (2022BKYZ035)。
文摘Sluggish reaction kinetics of oxygen evolution reaction(OER), resulting from multistep proton-coupled electron transfer and spin constriction, limits overall efficiency for most reported catalysts. Herein, using modeled ZnFe_(2-x)Ni_xO_(4)(0 ≤ x ≤ 0.4) spinel oxides, we aim to develop better OER electrocatalyst through combining the construction of ferromagnetic(FM) ordering channels and generation of highly active reconstructed species. The number of symmetry-breaking Fe–O–Ni structure links to the formation of FM ordering electron transfer channels. Meanwhile, as the number of Ni^(3+)increases, more ligand holes are formed, beneficial for redirecting surface reconstruction. The electro-activated ZnFe_(1.6)Ni_(0.4)O_(4) shows the highest specific activity, which is 13 and 2.5 times higher than that of ZnFe_(2)O_(4) and unactivated ZnFe_(1.6)Ni_(0.4)O_(4), and even superior to the benchmark IrO_(2) under the overpotential of 350 mV. Applying external magnetic field can make electron spin more aligned, and the activity can be further improved to 39 times of ZnFe_(2)O_(4). We propose that intriguing FM exchange-field interaction at FM/paramagnetic interfaces can penetrate FM ordering channels into reconstructed oxyhydroxide layers, thereby activating oxyhydroxide layers as spin-filter to accelerate spin-selective electron transfer. This work provides a new guideline to develop highly efficient spintronic catalysts for water oxidation and other spin-forbidden reactions.
基金Supported by National Science Council,Taiwan,China(Grant No.NSC 99-2221-E-006-253)
文摘The Antikythera mechanism is the most famous ancient astronomical calculator. The damaged excavation is a critical constraint for decoding the mechanism completely. By the systematic reconstruction design methodology, all feasible designs of the moon phase display device, which is one of the unclear mechanisms of the Antikythera mechanism, are reconstructed. These designs, including ordinary gear trains and epicyclic gear trains, are the simplest designs and satisfy the surviving evidence. The Antikythera mechanism and its reconstruction designs presented by LIN and YAN are introduced first. Three pointer types of the Antikythera mechanism are concluded based on their display motions and the orientation of the mechanism. In accordance with the analysis of the available interior reconstruction designs and the surviving evidence, four feasible designs of the moon phase display device are generated. All of them utilize the ball pointer with black and white that rotates around the radial axis to show cyclic moon phase. Two of these four feasible reconstruction designs are driven by one input source, and their bronze disks are fixed and rotatable respectively. Both of the remaining reconstruction designs are driven by two input sources, and their bronze disks are rotatable. Therefore, the four reconstruction designs of the moon phase display device reveal all possible display conditions of the moon phase pointers and the possible purposes of the bronze disk.
