RESUMEN

Lattice-oxygen activation has emerged as a popular strategy for optimizing the performance and selectivity of oxide-based thermocatalysis and electrolysis. However, the significance of lattice oxygen in oxide photocatalysts has been ignored, particularly in gas-solid reactions. Here, using methane oxidation over a Ru1@ZnO single-atom photocatalyst as the prototypical reaction and via 18O isotope labelling techniques, we found that lattice oxygen can directly participate in gas-solid reactions. Lattice oxygen played a dominant role in the photocatalytic reaction, as determined by estimating the kinetic constants in the initial stage. Furthermore, we discovered that dynamic diffusion between O2 and lattice oxygen proceeded even in the absence of targeted reactants. Finally, single-atom Ru can facilitate the activation of adsorbed O2 and the subsequent regeneration of consumed lattice oxygen, thus ensuring high catalyst activity and stability. The results provide guidance for next-generation oxide photocatalysts with improved activities and selectivities.

RESUMEN

The detection of volatile amines is necessary due to the serious toxicity hazards they pose to human skin, respiratory systems, and nervous systems. However, traditional amines detection methods require bulky equipment, high costs, and complex measurements. Herein, we report a new simple, rapid, convenient, and visual method for the detection of volatile amines based on the gas-solid reactions of tetrachloro-p-benzoquinone (TCBQ) and volatile amines. The gas-solid reactions of TCBQ with a variety of volatile amines showed a visually distinct color in a time-dependent manner. Moreover, TCBQ can be easily fabricated into simple and flexible rapid test strips for detecting and distinguishing n-propylamine from other volatile amines, including ethylamine, n-butyamine, n-pentamine, n-butyamine and dimethylamine, in less than 3 s without any equipment assistance.

RESUMEN

Gas-solid reactions are important for many redox processes that underpin the energy and sustainability transition. The specific case of hydrogen-based iron oxide reduction is the foundation to render the global steel industry fossil-free, an essential target as iron production is the largest single industrial emitter of carbon dioxide. This perception of gas-solid reactions has not only been limited by the availability of state-of-the-art techniques which can delve into the structure and chemistry of reacted solids, but one continues to miss an important reaction partner that defines the thermodynamics and kinetics of gas phase reactions: the gas molecules. In this investigation, cryogenic-atom probe tomography is used to study the quasi in situ evolution of iron oxide in the solid and gas phases of the direct reduction of iron oxide by deuterium gas at 700°C. So far several unknown atomic-scale characteristics are observed, including, D2 accumulation at the reaction interface; formation of a core (wüstite)-shell (iron) structure; inbound diffusion of D through the iron layer and partitioning of D among phases and defects; outbound diffusion of oxygen through the wüstite and/or through the iron to the next free available inner/outer surface; and the internal formation of heavy nano-water droplets at nano-pores.

RESUMEN

Nano-structured Mo/Fe intermetallics were synthesized from precursors that contained 72/28% and 30/70% molar ratios of Mo/Fe, which were given as precursors A and B, respectively. These precursors were prepared from the co-precipitation of aqueous hot solutions of ammonium heptamolybdate tetrahydrate (AHM) and ferrous oxalate. The dry precipitates were thermally treated using TG-DSC to follow up their behavior during roasting, in an Ar atmosphere of up to 700 °C (10° K/min). The TG profile showed that 32.5% and 55.5% weight losses were measured from the thermal treatment of precursors A and B, respectively. The DSC heat flow profile showed the presence of endothermic peaks at 196.9 and 392.5-400 °C during the thermal decomposition of the AHM and ferrous oxalate, respectively. The exothermic peak that was detected at 427.5 °C was due to the production of nano-sized iron molybdate [Fe2(MoO4)3]. An XRD phase analysis indicated that iron molybdate was the only phase that was identified in precursor A, while iron molybdate and Fe2O3 were produced in precursor B. Compacts were made from the pressing of the nano-sized precursors, which were roasted at 500 °C for 3 h. The roasted compacts were isothermally reduced in H2 at 600-850 °C using microbalance, and the O2 weight loss that resulted from the reduction reactions was continuously recorded as a function of time. The influence of the reduction temperature and precursor composition on the reduction behavior of the precursors was studied and discussed. The partially and completely reduced compacts were examined with X-ray powder diffraction (XRD), a reflected light microscope (RLM), and a scanning electron microscope (SEM-EDS). Depending on the precursor composition, the reduction reactions of the [Fe2(MoO4)3] and Fe2O3 proceeded through the formation of intermediate lower oxides, prior to the production of the MO/Fe intermetallic alloys. Based on the intermediate phases that were identified and characterized at the early, intermediate, and final reduction degrees, chemical reaction equations were given to follow up the formation of the MoFe and MoFe3 intermetallic alloys. The mechanism of the reduction reactions was predicted from the apparent activation energy values (Ea) that were computed at the different reduction degrees. Moreover, mathematical formulations that were derived from the gas-solid reaction model were applied to confirm the reduction mechanisms, which were greatly dependent on the precursor composition and reduction temperature. However, it can be reported that nano-structured MoFe and MoFe3 intermetallic alloys can be successfully fabricated via a gas-solid reaction technique at lower temperatures.

RESUMEN

As cellulose is the main polysaccharide in biomass, its degradation into glucose is a major undertaking in research concerning biofuels and bio-based platform chemicals. Here, we show that pressurized HCl gas is able to efficiently hydrolyze fibers of different crystalline forms (polymorphs) of cellulose when the water content of the fibers is increased to 30-50 wt%. Simultaneously, the harmful formation of strongly chromophoric humins can be suppressed by a simple addition of chlorite into the reaction system. 50-70 % glucose yields were obtained from cellulose I and II polymorphs while >90 % monosaccharide conversion was acquired from cellulose IIIII after a mild post-hydrolysis step. Purification of the products is relatively unproblematic from a gas-solid mixture, and a gaseous catalyst is easier to recycle than the aqueous counterpart. The results lay down a basis for future practical solutions in cellulose hydrolysis where side reactions are controlled, conversion rates are efficient, and the recovery of products and reagents is effortless.

Asunto(s)

Celulosa , Glucosa , Celulosa/química , Glucosa/química , Catálisis , Agua , Biomasa , Hidrólisis , Estrés Oxidativo

RESUMEN

Engineering the adsorption of molecules on active sites is an integral and challenging part for the design of highly efficient transition-metal-based catalysts for methanol dehydrogenation. A Mott-Schottky catalyst composed of Ni nanoparticles and tailorable nitrogen-doped carbon-foam (Ni/NCF) and thus tunable adsorption energy is presented for highly efficient and selective dehydrogenation of gas-phase methanol to hydrogen and CO even under relatively high weight hourly space velocities (WHSV). Both theoretical and experimental results reveal the key role of the rectifying contact at the Ni/NCF boundaries in tailoring the electron density of Ni species and enhancing the absorption energies of methanol molecules, which leads to a remarkably high turnover frequency (TOF) value (356 mol methanol mol-1 Ni h-1 at 350 °C), outpacing previously reported bench-marked transition-metal catalysts 10-fold.

RESUMEN

This study gives an account of an innovative, crucible-free technique for the synthesis of single-phase borides at relatively moderate temperatures. A metal wire heated by an electrical current reacts with a chosen gaseous boron halide in a gas/solid reaction yielding a single-phase, oxygen- and carbon-free product, as evidenced by X-ray powder diffraction and chemical analysis. This method is demonstrated using the example of hafnium reacting with boron tribromide. Preliminary thermodynamic considerations show that this kind of crucible-free synthesis specifically enables the preparation of borides of transition metals and similar elements.

RESUMEN

An integrated environmental cell has been designed and developed for the latest generation of Atom Probe Tomography LEAP™ instruments, allowing controlled exposure of samples to gases at high temperatures. Following treatment, samples can be transferred through the LEAP vacuum system for subsequent APT analysis, which provides detailed information on changes to chemical microstructures following the reactions with near-atomic resolution. A full description of the cell is presented, along with some sample results on the oxidation of aluminum and two platinum-group alloys, demonstrating the capability of combining exposure/characterization functionality in a single instrument.