Xiulian Pan

Iron Encapsulated within Pod-like Carbon Nanotubes for Oxygen Reduction Reaction

Chainmail for catalysts: a catalyst with iron nanoparticles confined inside pea-pod-like carbon nanotubes exhibits a high activity and remarkable stability as a cathode catalyst in polymer electrolyte membrane fuel cells (PEMFC), even in presence of SO(2). The approach offers a new route to electro- and heterogeneous catalysts for harsh conditions.

Effect of Confinement in Carbon Nanotubes on the Activity of Fischer−Tropsch Iron Catalyst

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.

Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen

Upgrading Methane Sans Oxygen Direct routes to converting methane to higher hydrocarbons can allow natural gas to be used to provide chemical feedstocks. However, the reaction conditions needed to activate the strong C-H bond tend to overoxidize the products. Guo et al. (p. 616) report a high-temperature nonoxidative route that exposes methane to isolated iron sites on a silica catalyst. Methyl radicals were generated and coupled in the gas phase to form ethylene and aromatics along with hydrogen. The isolation of the active sites avoided surface reactions between the radicals that would deposit solid carbon. Methyl radicals that form at isolated iron sites in a silica matrix form gas-phase products and do not deposit solid carbon. 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.

The Effects of Confinement inside Carbon Nanotubes on Catalysis

The unique tubular morphology of carbon nanotubes (CNTs) has triggered wide research interest. These structures can be used as nanoreactors and to create novel composites through the encapsulation of guest materials in their well-defined channels. The rigid nanotubes restrict the size of the encapsulated materials down to the nanometer and even the sub-nanometer scale. In addition, interactions may develop between the encapsulated molecules and nanomaterials and the CNT surfaces. The curvature of CNT walls causes the π electron density of the graphene layers to shift from the concave inner to the convex outer surface, which results in an electric potential difference. As a result, the molecules and nanomaterials on the exterior walls of CNTs likely display different properties and chemical reactivities from those confined within CNTs. Catalysis that utilizes the interior surface of CNTs was only explored recently. An increasing number of studies have demonstrated that confining metal or metal oxide nanoparticles inside CNTs often leads to a different catalytic activity with respect to the same metals deposited on the CNT exterior surface. Furthermore, this inside and outside activity difference varies based on the metals used and the reactions catalyzed. In this Account, we describe the efforts toward understanding the fundamental effects of confining metal nanoparticles inside the CNT channels. This research may provide a novel approach to modulate their catalytic performance and promote rational design of catalysts. To achieve this, we have developed strategies for homogeneous dispersion of nanoparticles inside nanotubes. Because researchers have previously demonstrated the insertion of nanoparticles within larger nanotubes, we focused specifically on multiwalled carbon nanotubes (MWCNTs) with an inner diameter (i.d.) smaller than 10 nm and double-walled carbon nanotubes (DWCNTs) with 1.0-1.5 nm i.d. The results show that CNTs with well-defined morphology and unique electronic structure of CNTs provide an intriguing confinement environment for catalysis.

Selective conversion of syngas to light olefins.

Small olefins from syngas The conversion of coal or natural gas to liquid fuels or chemicals often proceeds through the production of CO and H2. This mixture, known as syngas, is then converted to hydrocarbons with Fischer-Tropsch catalysts. For the light olefins (ethylene to butylenes) needed for chemical and polymer synthesis, conventional catalysts are mechanistically limited to <60% conversion and deactivate through carbon buildup. Jiao et al. developed a bifunctional catalyst that achieves higher conversions and avoids deactivation (see the Perspective by de Jong). A zinc-chromium oxide creates ketene intermediates that are then coupled over a zeolite. Science, this issue p. 1065, see also p. 1030 A composite catalyst circumvents conventional limitations on the Fischer-Tropsch synthesis of light olefins from syngas. [Also see Perspective by de Jong] 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 (ZnCrOx) 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.

Reactions over catalysts confined in carbon nanotubes

We review a new concept for modifying the redox properties of transition metals via confinement within the channels of carbon nanotubes (CNTs), and thus tuning their catalytic performance. Attention is also devoted to novel techniques for homogeneous dispersion of metal nanoparticles inside CNTs since these are essential for optimization of the catalytic activity.

A single iron site confined in a graphene matrix for the catalytic oxidation of benzene at room temperature.

A coordinatively unsaturated single iron site confined in a graphene matrix shows an ultrahigh activity for catalytic oxidation. Coordinatively unsaturated (CUS) iron sites are highly active in catalytic oxidation reactions; however, maintaining the CUS structure of iron during heterogeneous catalytic reactions is a great challenge. Here, we report a strategy to stabilize single-atom CUS iron sites by embedding highly dispersed FeN4 centers in the graphene matrix. The atomic structure of FeN4 centers in graphene was revealed for the first time by combining high-resolution transmission electron microscopy/high-angle annular dark-field scanning transmission electron microscopy with low-temperature scanning tunneling microscopy. These confined single-atom iron sites exhibit high performance in the direct catalytic oxidation of benzene to phenol at room temperature, with a conversion of 23.4% and a yield of 18.7%, and can even proceed efficiently at 0°C with a phenol yield of 8.3% after 24 hours. Both experimental measurements and density functional theory calculations indicate that the formation of the Fe═O intermediate structure is a key step to promoting the conversion of benzene to phenol. These findings could pave the way toward highly efficient nonprecious catalysts for low-temperature oxidation reactions in heterogeneous catalysis and electrocatalysis.

Probing the Electronic Effect of Carbon Nanotubes in Catalysis: NH3 Synthesis with Ru Nanoparticles

Carbon nanotubes (CNTs) have been shown to modify some properties of nanomaterials and to modify chemical reactions confined inside their channels, which are formed by curved graphene layers. Here we studied ammonia synthesis over Ru as a probe reaction to understand the effect of the electron structure of CNTs on the confined metal particles and their catalytic activity. The catalyst with Ru nanoparticles dispersed almost exclusively on the exterior nanotube surface exhibits a higher activity than the CNT-confined Ru, although both have a similar metal particle size. Characterization with TEM, N(2) physisorption, H(2) chemisorption, temperature-programmed reduction, CO adsorption microcalorimetry, and first-principles calculations suggests that the outside Ru exhibits a higher electron density than the inside Ru. As a result, the dissociative adsorption of N(2), which is an electrophilic process and the rate-determining step of ammonia synthesis, is more facile over the outside Ru than that over the inside one.

Size effect of graphene on electrocatalytic activation of oxygen

Crystals of graphite nanosheets, achieved via a simple ball milling approach, show a significant size effect in electrocatalytic activation of oxygen.

Tailored cutting of carbon nanotubes and controlled dispersion of metal nanoparticles inside their channels

A novel method has been developed for homogeneous dispersion of metal nanoparticles inside short carbon nanotubes (CNTs) with an inner diameter smaller than 10 nm. The process involves controlled cutting of pristine long nanotubesviaoxidation catalyzed by Ag or Fe and introduction of metal nanoparticles inside the CNT channels using a wet chemistry method aided by ultrasonic treatment and extended stirring. The resulting metal particles are very uniform with sizes in the range of 2–4 nm. In addition, selective dispersion of such nanoparticles on the exterior surfaces of open CNTs has been achieved by temporary blocking of the channels with an organic solvent while decorating the CNT exterior surfaces with aqueous solution of the metal salt. The trick is the choice of this organic solvent, which is immiscible with, and has a higher boiling point than, water.