Mesoporous hollow carbon spheres (MHCSs) were synthesized (d = 290 nm; carbon shell 20−35 nm), and their hollow morphology was exploited to study the influence of Ru nanoparticle location relative to Co3O4 nanoparticles on the reduction behavior and activity of Co Fischer−Tropsch catalysts. Ru nanoparticles were loaded both inside and outside the MHCS, while Co3O4 particles (ca. Co 15 wt % loading) were loaded on the outside of the MHCS. The use of in situ powder X-ray diff raction (PXRD) and temperaturepro-grammed reduction studies on the catalysts indicated the eff ect of Ru location on the Co3O4 reduction pathways. A secondary hydrogen spillover eff ect was invoked to explain a complete reduction of the Co3O4 on Ru@MHCS@Co at 450 °C. Secondary hydrogen spillover enhanced the CoO to Co transformation by lowering the reduction temperature when compared to the unpromoted catalyst. Primary hydrogen spillover was inferred to explain the complete reduction of Co3O4 to Co metal on CoRu/MHCS at 300 °C. After catalyst activation at 350 °C, the primary spillover process yielded a catalyst with higher Fischer−Tropsch activity (ca. 2×) than the unpromoted catalyst and the catalysts where Ru and Co were separated by the mesoporous carbon shell. This was partially related to the Co phases that formed on the carbon support during reduction and the catalyst degree of reduction that was reliant on the type of hydrogen spillover process.

Carbon spheres (CSs) synthesised by the hydrothermal approach were explored as a model support material for a bimetallic Fe–Co Fischer–Tropsch (FT) catalyst. The CSs were characterised by N2 adsorption–desorption, thermogravimetric analysis, FTIR spectroscopy and powder XRD. If annealed at 900 °C for 4 h, the CSs exhibited an improved surface area, thermal stability and crystallinity. A series of Fe–Co bimetallic FT catalysts supported on the annealed CSs were prepared by co‐precipitation. A variety of Fe‐to‐Co ratios were used with the total metal loadings maintained at 10 %. Catalyst reducibility studies were performed by H2 temperature‐programmed reduction and in situ powder XRD. Catalysts with a Fe/Co ratio of 5:5 (w/w) showed Co–Fe alloy formation upon reduction at >450 °C. Interestingly, the presence of this alloy did not correlate with high C5+ selectivities during FT synthesis; rather the Co‐rich/Fe‐poor catalyst gave the best selectivity. The CSs allowed the metal–metal interactions in the bimetallic systems to be monitored because of the weak interaction of the metals with the support.

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In this study the outer surface of porous hollow carbon spheres (HCSs) materials were functionalized by N-doping using a post-synthesis method and they were used as a Fischer-Tropsch catalyst support. Melamine was used as the nitrogen source, and carbonization was performed at diff erent temperatures (600 and 900 °C) to introduce variable levels of N into the HCSs, with diff erent bonding configurations. This procedure allowed for the incorporation of up to 13% N. Our results show that post-synthesis N-doping introduced marginal defects into the carbon framework and this did not aff ect the thermal stability of the materials. XPS studies revealed that the surface content on these materials varied and provided evidence for temperaturetunable bonding configurations. Eff ects associated with post-synthesis N-doping were apparent on the Co catalyst (˜10 wt.%) properties such as the inhibited reduction caused by a metal-support interaction observed by the H2-TPR and in situ PXRD techniques. As a consequence the Fischer-Tropsch performance was influenced as both the activity and stability were improved on the catalysts supported on the N-doped materials. TEM analysis of the spent catalysts demonstrated the influence of N-doping on the sintering characteristics of Co, with particles > 30 nm measured on the N-free catalyst while Ndoped samples had sizes < 15 nm.

The solar-driven reduction of nitrate to nitrogen has been studied in the presence of a formate hole scavenger, over a series of Au- and Ag-decorated TiO2 catalysts.

Mesoporous carbon spheres (CSs-H) were hydrothermally synthesised using sugar as carbon source. The as-synthesized CSs-H was microporous but after thermal treatment at 900 °C for 4 h it became mesoporous (surface area of 463 m 2 g −1 ). Further treatment of the annealed CSs-H with HNO 3 gave a functionalized CSs-H with a high defect content in the carbon matrix which resulted in an increase in surface area (509 m 2 g −1 ). The functionalized and un-functionalized CSs-H were used to support nano Ru particles for CO, CO 2 and selective CO methanation reactions. The Ru supported catalysts were prepared using both impregnation and microwave polyol synthesis methods. It was evident from the reduction studies that the functional groups on the surface of the CSs-H influenced the reduction of the RuO 2 to Ru. The catalyst with smaller and well dispersed RuO 2 particles (d = 2.7 nm) (prepared by the microwave polyol technique) gave a high activity in both CO and selective CO methanation studies. The larger Ru particles observed on the un-functionalized CSs-H showed poor activity for CO and selective CO methanation reactions and also did not promote the reverse water gas shift reaction. Graphical Abstract

A B S T R A C TOne of the major set-backs in the selective CO methanation process, as the final clean-up step in removing residual CO from reformate gas feed, is the reverse water gas shift (RWGS) reaction. This reaction is an undesired reaction because, it runs parallel with the selective CO methanation reaction. This increases the CO outlet concentration. The catalytic performance of ruthenium supported on carbon nanotubes (CNTs), nitrogen doped carbon nanotubes (NCNTs), titania coated carbon nanotubes (NCNT-TiO2 and CNTs-TiO2) and TiO2 anatase (TiO2-A) for selective CO methanation was investigated. The feed composition relevant to reformate gas was used but in the absence of steam. The experiments were conducted within a temperature range of 100 °C and 360 °C. It was observed that carbon dioxide methanation was suppressed until CO methanation attained a maximum conversion for all the catalysts studied. The Ru/NCNT showed higher activity than Ru/CNT at all temperatures examined due to the nitrogen incorporation in the carbon domains. Both Ru/CNT and Ru/NCNT however promoted the RWGS reaction at temperatures above 250 °C. The Ru/CNT-TiO2 catalyst recorded the highest activity for both the CO and selective CO methanation followed by Ru/TiO2-A. The presence of titania on the carbon nanotubes significantly retarded the RWGS reaction from about −120% CO conversion to about 80% CO conversion, while selectivity towards methane increased in all catalysts with increasing temperature.