Mingming Wei

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.

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.

Reversible structural transformation of FeOx nanostructures on Pt under cycling redox conditions and its effect on oxidation catalysis

Understanding dynamic changes of catalytically active nanostructures under reaction conditions is a pivotal challenge in catalysis research, which has been extensively addressed in metal nanoparticles but is less explored in supported oxide nanocatalysts. Here, structural changes of iron oxide (FeO(x)) nanostructures supported on Pt in a gaseous environment were examined by scanning tunneling microscopy, ambient pressure X-ray photoelectron spectroscopy, and in situ X-ray absorption spectroscopy using both model systems and real catalysts. O-Fe (FeO) bilayer nanostructures can be stabilized on Pt surfaces in reductive environments such as vacuum conditions and H2-rich reaction gas, which are highly active for low temperature CO oxidation. In contrast, exposure to H2-free oxidative gases produces a less active O-Fe-O (FeO2) trilayer structure. Reversible transformation between the FeO bilayer and FeO2 trilayer structures can be achieved under alternating reduction and oxidation conditions, leading to oscillation in the catalytic oxidation performance.

Architecture of PtFe/C catalyst with high activity and durability for oxygen reduction reaction

A PtFe/C catalyst has been synthesized by impregnation and high-temperature reduction followed by acid-leaching. X-ray diffraction, X-ray photoelectron spectroscopy and X-ray atomic near edge spectroscopy characterization reveal that Pt3Fe alloy formation occurs during high-temperature reduction and that unstable Fe species are dissolved into acid solution. The difference in Fe concentration from the core region to the surface and strong O-Fe bonding may drive the outward diffusion of Fe to the highly corrugated Pt-skeleton, and the resulting highly dispersed surface FeOx is stable in acidic medium, leading to the construction of a Pt3Fe@Pt-FeOx architecture. The as prepared PtFe/C catalyst demonstrates a higher activity and comparable durability for the oxygen reduction reaction compared with a Pt/C catalyst, which might be due to the synergetic effect of surface and subsurface Fe species in the PtFe/C catalyst.

Simultaneous N-intercalation and N-doping of epitaxial graphene on 6H-SiC(0001) through thermal reactions with ammonia

AbstractSurface functionalization of epitaxial graphene overlayers on 6H-SiC(0001) has been attempted through thermal reactions in NH3. X-ray photoelectron spectroscopy and micro-region low energy electron diffraction results show that a significant amount of N is present at the NH3-treated graphene surface, which results in strong band bending at the SiC surface as well as decoupling of the graphene overlayers from the substrate. The majority of the surface N species can be removed by annealing in vacuum up to 850 °C, weakening the surface band bending and resuming the strong coupling of graphene with the SiC surface. The desorbed N atoms can be attributed to the intercalated species between graphene and SiC. Low temperature scanning tunneling spectroscopy and density functional theory simulations confirm the presence of N dopants in the graphene lattice, which are in the form of graphitic substitution and can be stable above 850 °C. This is the first report of simultaneous N intercalation and N doping of epitaxial graphene overlayers on SiC, and it may be employed to alter the surface physical and chemical properties of epitaxial graphene overlayers.

Stability of BN/metal interfaces in gaseous atmosphere

AbstractHexagonal boron nitride (h-BN) is often prepared by epitaxial growth on metals, and stability of the formed BN/metal interfaces in gaseous environment is a key issue for physicochemical properties of the BN overlayers. As an illustration here, the structural change of a BN/Ru(0001) interface upon exposure to O2 has been investigated using in situ photoemission electron microscopy (PEEM) and ambient pressure X-ray photoelectron spectroscopy (AP-XPS). We demonstrate the occurrence of oxygen intercalation of the BN overlayers in O2 atmosphere, which decouples the BN overlayer from the substrate. Comparative studies of oxygen intercalation at BN/Ru(0001) and graphene/Ru(0001) surfaces indicate that the oxygen intercalation of BN overlayers happens more easily than graphene. This finding will be of importance for future applications of BN-based devices and materials under ambient conditions.

Comparative studies of redox behaviors of Pt-Co/SiO2 and Au-Co/SiO2 catalysts and their activities in CO oxidation

Silica supported Pt–Co and Au–Co nanoparticles (NPs) were subjected to various redox processes and characterized by X-ray diffraction, X-ray absorption near edge structure, and X-ray photoelectron spectroscopy. We found that most of the Co oxide (CoOx) species on Pt NPs can be reduced at 100 °C forming an alloy structure with Pt at elevated temperatures. Oxidation of Co in the reduced sample takes place gradually with increasing temperatures. In contrast, temperatures higher than 400 °C are needed to reduce CoOx on Au NPs and Co atoms hardly form an alloy with Au even at 600 °C. The Co species in the reduced Au–Co/SiO2 sample were quickly oxidized in an O2 atmosphere at room temperature. High CO oxidation activity was observed in the Pt–Co/SiO2 catalyst reduced below 300 °C; however this necessitated reduction at 600 °C of the Au–Co/SiO2 catalyst. The results illustrate a stronger interaction of Co (CoOx) with Pt than with Au. In both systems, the optimum treatment conditions are to produce a similar CoO-on-noble metal (NM) active structure and maximize the density of interface sites between the surface CoO structure and the NM support.

Graphene as a surfactant for metal growth on solid surfaces: Fe on graphene/SiC(0001)

X-ray photoelectron spectroscopic and scanning tunneling microscopic results demonstrate that annealing of Fe/carbon-rich 6H-SiC(0001) surface between 650 and 750 °C leads to Fe intercalation under the surface carbon layer. Accompanied with the metal intercalation, the carbon nanomesh surface was transformed into a graphene surface. Moreover, the formed graphene layers always float out to the topmost surface even after deposition of more than 10 monolayer Fe, acting as a surfactant. Using graphene as the surfactant may not only promote the 2D growth but also can improve the film performance considering that graphene is stable and robust.