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We first studied the reactivity of H2O vapor in metal–organic frameworks (MOFs) with Pt nanocrystals (NCs) through the water–gas shift (WGS) reaction. A water‐stable MOF, UiO‐66, serves as a highly effective support material for the WGS reaction compared with ZrO2. The origin of the high catalytic performance was investigated using in situ IR spectroscopy. In addition, from a comparison of the catalytic activities of Pt on UiO‐66, where Pt NCs are located on the surface of UiO‐66 and Pt@UiO‐66, where Pt NCs are coated with UiO‐66, we found that the competitive effects of H2O condensation and diffusion in the UiO‐66 play important roles in the catalytic activity of Pt NCs. A thinner UiO‐66 coating further enhanced the WGS reaction activity of Pt NCs by minimizing the negative effect of slow H2O diffusion in UiO‐66.  相似文献   
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We report the synthesis of high-entropy-alloy (HEA) nanoparticles (NPs) consisting of five platinum group metals (Ru, Rh, Pd, Ir and Pt) through a facile one-pot polyol process. We investigated the electronic structure of HEA NPs using hard X-ray photoelectron spectroscopy, which is the first direct observation of the electronic structure of HEA NPs. Significantly, the HEA NPs possessed a broad valence band spectrum without any obvious peaks. This implies that the HEA NPs have random atomic configurations leading to a variety of local electronic structures. We examined the hydrogen evolution reaction (HER) and observed a remarkably high HER activity on HEA NPs. At an overpotential of 25 mV, the turnover frequencies of HEA NPs were 9.5 and 7.8 times higher than those of a commercial Pt catalyst in 0.05 M H2SO4 and 1.0 M KOH electrolytes, respectively. Moreover, the HEA NPs showed almost no loss during a cycling test and were much more stable than the commercial Pt catalyst. Our findings on HEA NPs may provide a new paradigm for the design of catalysts.

RuRhPdIrPt high-entropy-alloy nanoparticles with a broad and featureless valence band spectrum show high hydrogen evolution reaction activity.  相似文献   
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A newly synthesized one‐dimensional (1D) hydrogen‐bonded (H‐bonded) rhodium(II)–η5‐semiquinone complex, [Cp*Rh(η5p‐HSQ‐Me4)]PF6 ([ 1 ]PF6; Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl; HSQ=semiquinone) exhibits a paraelectric–antiferroelectric second‐order phase transition at 237.1 K. Neutron and X‐ray crystal structure analyses reveal that the H‐bonded proton is disordered over two sites in the room‐temperature (RT) phase. The phase transition would arise from this proton disorder together with rotation or libration of the Cp* ring and PF6? ion. The relative permittivity εb′ along the H‐bonded chains reaches relatively high values (ca., 130) in the RT phase. The temperature dependence of 13C CP/MAS NMR spectra demonstrates that the proton is dynamically disordered in the RT phase and that the proton exchange has already occurred in the low‐temperature (LT) phase. Rate constants for the proton exchange are estimated to be 10?4–10?6 s in the temperature range of 240–270 K. DFT calculations predict that the protonation/deprotonation of [ 1 ]+ leads to interesting hapticity changes of the semiquinone ligand accompanied by reduction/oxidation by the π‐bonded rhodium fragment, producing the stable η6‐hydroquinone complex, [Cp*Rh3+6p‐H2Q‐Me4)]2+ ([ 2 ]2+), and η4‐benzoquinone complex, [Cp*Rh+4p‐BQ‐Me4)] ([ 3 ]), respectively. Possible mechanisms leading to the dielectric response are discussed on the basis of the migration of the protonic solitons comprising of [ 2 ]2+ and [ 3 ], which would be generated in the H‐bonded chain.  相似文献   
6.
The enhancement of the light absorption ability of synthetic chlorophyll derivatives is demonstrated. Chlorophyll derivatives directly conjugated with a difluoroboron 1,3‐diketonate group at the C3 position were synthesized from methyl pyropheophorbide‐d through Barbier acylmethylation of the C3‐formyl moiety, oxidation of the C3‐carbinol, and difluoroboron complexation of the diketonate. Electronic absorption spectra in a diluted solution showed that the synthetic conjugates gave an absorption band at λ=400–500 nm, with a Qy band shifted to a longer wavelength of λ≈700 nm. DFT calculations demonstrated that the absorption bands and redshifts were ascribable to the coupling of the LUMO of chlorin with that of the difluoroboron diketonate moiety. The introduction of a pyrenyl group at the C33‐position of the conjugate afforded an additional charge‐transfer band over λ=500 nm, producing a pigment that bridged the green gap in standard chlorophylls.  相似文献   
7.
Simultaneous manipulation of both spin and charge is a crucial issue in magnetic conductors. We report on a strong correlation between magnetism and conductivity in the iodine‐bonded molecular conductor (DIETSe)2FeBr2Cl2 [DIETSe=diiodo(ethylenedithio)tetraselenafulvalene], which is the first molecular conductor showing a large hysteresis in both magnetic moment and magnetoresistance associated with a spin‐flop transition. Utilizing a mixed‐anion approach and iodine bonding interactions, we tailored a molecular conductor with random exchange interactions exhibiting unforeseen physical properties.  相似文献   
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Two salts of the aromatic hydrocarbon decacyclene, {cryptand[2.2.2](Cs+)} (decacyclene.?) ( 1 ) and {Bu3MeP+}(decacyclene.?) ( 2 ), were obtained. In both salts, decacyclene.? radical anions formed channels occupied by cations. However, corrugated hexagonal decacyclene.? layers could be outlined in the crystal structure of 1 with several side‐by‐side C???C approaches. The decacyclene.? radical anions showed strong distortion in both salts, deviating from the C3 symmetry owing to the repulsion of closely arranged hydrogen atoms and the Jahn‐Teller effect. Radical anions showed intense unusually low energy absorption in the IR‐range, with maxima at 4800 and 6000 cm?1. According to the carculations, these bands can originate from the SOMO‐LUMO+1 and SOMO‐LUMO+2 transitions, respectively. Radical anions exhibited a S=1/2 spin state, with an effective magnetic moment of 1.72 μB at 300 K. The decacyclene.? spin antiferromagnetically coupled with a Weiss temperature of ?11 K. Spin ordering was not observed down to 1.9 K owing to spin frustration in the hexagonal decacyclene.? layers.  相似文献   
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