The efficient use of natural gas will require catalysts that can activate the first C-H bond of methane while suppressing complete dehydrogenation and avoiding overoxidation. We report that single iron sites embedded in a silica matrix enable direct, nonoxidative conversion of methane, exclusively to ethylene and aromatics. The reaction is initiated by catalytic generation of methyl radicals, followed by a series of gas-phase reactions. The absence of adjacent iron sites prevents catalytic C-C coupling, further oligomerization, and hence, coke deposition. At 1363 kelvin, methane conversion reached a maximum at 48.1% and ethylene selectivity peaked at 48.4%, whereas the total hydrocarbon selectivity exceeded 99%, representing an atom-economical transformation process of methane. The lattice-confined single iron sites delivered stable performance, with no deactivation observed during a 60-hour test.

Although considerable progress has been made in direct synthesis gas (syngas) conversion to light olefins (C2(=)-C4(=)) via Fischer-Tropsch synthesis (FTS), the wide product distribution remains a challenge, with a theoretical limit of only 58% for C2-C4 hydrocarbons. We present a process that reaches C2(=)-C4(=) selectivity as high as 80% and C2-C4 94% at carbon monoxide (CO) conversion of 17%. This is enabled by a bifunctional catalyst affording two types of active sites with complementary properties. The partially reduced oxide surface (ZnCrO(x)) activates CO and H2, and C-C coupling is subsequently manipulated within the confined acidic pores of zeolites. No obvious deactivation is observed within 110 hours. Furthermore, this composite catalyst and the process may allow use of coal- and biomass-derived syngas with a low H2/CO ratio.

Chainmail for catalysts: A catalyst with iron nanoparticles confined inside pea‐pod‐like carbon nanotubes (see picture) exhibits a high activity and remarkable stability as a cathode catalyst in polymer electrolyte membrane fuel cells (PEMFC), even in presence of SO2. The approach offers a new route to electro‐ and heterogeneous catalysts for harsh conditions.

The quest for an efficient process to convert methane efficiently to fuels and high value-added chemicals such as olefins and aromatics is motivated by their increasing demands and recently discovered large reserves and resources of methane. Direct conversion to these chemicals can be realized either oxidatively via oxidative coupling of methane (OCM) or nonoxidatively via methane dehydroaromatization (MDA), which have been under intensive investigation for decades. While industrial applications are still limited by their low yield (selectivity) and stability issues, innovations in new catalysts and concepts are needed. The newly emerging strategy using iron single sites to catalyze methane conversion to olefins, aromatics, and hydrogen (MTOAH) attracted much attention when it was reported. Because the challenge lies in controlled dehydrogenation of the highly stable CH and selective C-C coupling, we focus mainly on the fundamentals of C-H activation and analyze the reaction pathways toward selective routes of OCM, MDA, and MTOAH. With this, we intend to provide some insights into their reaction mechanisms and implications for future development of highly selective catalysts for direct conversion of methane to high value-added chemicals.

Following our previous findings that confinement within carbon nanotubes (CNTs) can modify the redox properties of encapsulated iron oxides, we demonstrate here how this can affect the catalytic reactivity of iron catalysts in Fischer-Tropsch synthesis (FTS). The investigation, using in situ XRD under conditions close to the reaction conditions, reveals that the distribution of iron carbide and oxide phases is modulated in the CNT-confined system. The iron species encapsulated inside CNTs prefer to exist in a more reduced state, tending to form more iron carbides under the reaction conditions, which have been recognized to be essential to obtain high FTS activity. The relative ratio of the integral XRD peaks of iron carbide (Fe(x)C(y)) to oxide (FeO) is about 4.7 for the encapsulated iron catalyst in comparison to 2.4 for the iron catalyst dispersed on the outer walls of CNTs under the same conditions. This causes a remarkable modification of the catalytic performance. The yield of C5+ hydrocarbons over the encapsulated iron catalyst is twice that over iron catalyst outside CNTs and more than 6 times that over activated-carbon-supported iron catalyst. The catalytic activity enhancement is attributed to the effect of confinement of the iron catalyst within the CNT channels. As demonstrated by temperature-programmed reduction in H2 and in CO atmospheres, the reducibility of the iron species is significantly improved when they are confined. The ability to modify the redox properties via confinement in CNTs is expected to be of significance for many catalytic reactions, which are highly dependent on the redox state of the active components. Furthermore, diffusion and aggregation of the iron species through the reduction and reaction have been observed, but these are retarded inside CNTs due to the spatial restriction of the channels.

Theoretical studies predicted that doping graphene with nitrogen can tailor its electronic properties and chemical reactivity. However, experimental investigations are still limited because of the lack of synthesis techniques that can deliver a reasonable quantity. We develop here a novel method for one-pot direct synthesis of N-doped graphene via the reaction of tetrachloromethane with lithium nitride under mild conditions, which renders fabrication in gram scale. The distinct electronic structure perturbation induced by the incorporation of nitrogen in the graphene network is observed for the first time by scanning tunnelling microscopy. The nitrogen content varies in the range of 4.5−16.4%, which allows further modulation of the properties. The enhanced catalytic activity is demonstrated in a fuel cell cathode oxygen reduction reaction with respect to pure graphene and commercial carbon black XC-72. The resulting N-doped materials are expected to broaden the already widely explored potential applications for graphene.

Carbon nanotubes (CNTs) have well-defined hollow interiors and exhibit unusual mechanical and thermal stability as well as electron conductivity. This opens intriguing possibilities to introduce other matter into the cavities, which may lead to nanocomposite materials with interesting properties or behaviour different from the bulk. Here, we report a striking enhancement of the catalytic activity of Rh particles confined inside nanotubes for the conversion of CO and H2 to ethanol. The overall formation rate of ethanol (30.0 mol mol(-1)Rh h(-1)) inside the nanotubes exceeds that on the outside of the nanotubes by more than an order of magnitude, although the latter is much more accessible. Such an effect with synergetic confinement has not been observed before in catalysis involving CNTs. We believe that our discovery may be of a quite general nature and could apply to many other processes. It is anticipated that this will motivate theoretical and experimental studies to further the fundamental understanding of the host-guest interaction within carbon and other nanotube systems.

A coordinatively unsaturated single iron site confined in a graphene matrix shows an ultrahigh activity for catalytic oxidation.