Formation mechanism of highly dispersed semi-embedded ruthenium nanoparticles in porous carbon matrix determined by in situ temperature-programmed infrared spectroscopy

The carbonization process of a sucrose‐RuCl3/SBA‐15composite towards a Ru‐containing ordered mesoporous carbon(Ru‐OMC)catalyst was studied by in situ temperature‐programmed infrared spectroscopy to identify the stabilization role of organic carbon precursors during the formation of highly dispersed Ru nanoparticles.The results show that the formation of metal carbonyl species results in the formation of homogeneously distributed Ru nanoparticles,and the rigid silica support and carbon matrix around the Ru(CO)x complex can significantly avoid the sintering and agglomeration of Ru metal particles during elevated temperature thermal treatment.These results ultimately demonstrate that sucrose plays important roles in the formation of homogeneously distributed Ru nanoparticles in a porous carbon matrix.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Synergistically boosting the elementary reactions over multiheterogeneous ordered macroporous Mo2C/NC-Ru for highly efficient alkaline hydrogen evolution

Simultaneously enhancing the reaction kinetics,mass transport,and gas release during alkaline hydrogen evolution reaction(HER)is critical to minimizing the reaction polarization resistance,but remains a big challenge.Through rational design of a hierarchical multiheterogeneous three-dimensionally(3D)ordered macroporous Mo_(2)C-embedded nitrogen-doped carbon with ultrafine Ru nanoclusters anchored on its surface(OMS Mo_(2)C/NC-Ru),we realize both electronic and morphologic engineering of the catalyst to maximize the electrocatalysis performance.The formed Ru-NC heterostructure shows regulative electronic states and optimized adsorption energy with the intermediate H*,and the Mo_(2)C-NC heterostructure accelerates the Volmer reaction due to the strong water dissociation ability as confirmed by theoretical calculations.Consequently,superior HER activity in alkaline solution with an extremely low overpotential of 15.5 mV at 10 mAcm^(−2)with the mass activity more than 17 times higher than that of the benchmark Pt/C,an ultrasmall Tafel slope of 22.7 mV dec−1,and excellent electrocatalytic durability were achieved,attributing to the enhanced mass transport and favorable gas release process endowed from the unique OMS Mo_(2)C/NC-Ru structure.By oxidizing OMS Mo_(2)C/NC-Ru into OMS MoO_(3)-RuO_(2)catalyst,it can also be applied as efficient oxygen evolution electrocatalyst,enabling the construction of a quasi-symmetric electrolyzer for overall water splitting.Such a device's performance surpassed the state-of-the-art Pt/C||RuO2 electrolyzer.This study provides instructive guidance for designing 3D-ordered macroporous multicomponent catalysts for efficient catalytic applications.

Constructing a hollow core-shell structure of RuO_(2) wrapped by hierarchical porous carbon shell with Ru NPs loading for supercapacitor

Hollow core-shell structure nanomaterials have been broadly used in energy storage, catalysis, reactor,and other fields due to their unique characteristics, including the synergy between different materials,a large specific surface area, small density, large charge carrying capacity and so on. However, their synthesis processes were mostly complicated, and few researches reported one-step encapsulation of different valence states of precious metals in carbon-based materials. Hence, a novel hollow core-shell nanostructure electrode material, RuO_(2)@Ru/HCs, with a lower mass of ruthenium to reduce costs was constructed by one-step hydrothermal method with hard template and co-assembled strategy, consisting of RuO_(2) core and ruthenium nanoparticles(Ru NPs) in carbon shell. The Ru NPs were uniformly assembled in the carbon layer, which not only improved the electronic conductivity but also provided more active centers to enhance the pseudocapacitance. The RuO_(2) core further enhanced the material’s energy storage capacity. Excellent capacitance storage(318.5 F·g^(-1)at 0.5 A·g^(-1)), rate performance(64.4%) from 0.5 A·g^(-1)to 20 A·g^(-1), and cycling stability(92.3% retention after 5000 cycles) were obtained by adjusting Ru loading to 0.92%(mass). It could be attributed to the wider pore size distribution in the micropores which increased the transfer of electrons and protons. The symmetrical supercapacitor device based on RuO_(2)@Ru/HCs could successfully light up the LED lamp. Therefore, our work verified that interfacial modification of RuO_(2) and carbon could bring attractive insights into energy density for nextgeneration supercapacitors.

Catalytic combustion of soot over Ru-doped mixed oxides catalysts

We employed modified substrates as outer heterogeneous catalysts to reduce the soot originating from the incomplete diesel combustion. Here, we proposed that ceria（CeO2）-based catalysts could lower the temperature at which soot combustion occurred from 610 oC to values included in the operation range of diesel exhausts（270–400 oC）. Here, we used the sol-gel method to synthesize catalysts based on mixed oxides（ZnO：CeO2） deposited on cordierite substrates, and modified by ruthenium nanoparticles. The presence of ZnO in these mixed oxides produced defects associated with oxygen vacancies, improving thermal stability, redox potential, sulfur resistance, and oxygen storage. We evaluated the morphological and structural properties of the material by X-ray diffraction（XRD）, Brumauer-emmett-teller method（BET）, temperature programmed reduction（H2-TPR）, scanning electron microscopy（SEM）, and transmission electron microscopy（TEM）. We investigated how the addition of Ru（0.5 wt.%） affected the catalytic activity of ZnO：CeO2 in terms of soot combustion. Thermogravimetric analysis（TG/DTA） revealed that presence of the catalyst decreased the soot combustion temperature by 250 oC, indicating that the oxygen species arose at low temperatures, which was the main reason for the high reactivity of the oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy（DRS） showed that the catalyst containing Ru on the mixed oxide-impregnated cordierite samples efficiently oxidized soot in a diesel stationary motor： soot emission decreased 80%.