RESUMO
Two-dimensional hydrogen boride (HB) sheets were recently demonstrated to act as a solid acid catalyst in their hydrogen-deficient state. However, both the active sites and the mechanism of the catalytic process require further elucidation. In this study, we analyzed the conversion of ethanol adsorbed on HB sheets under vacuum during heating using in situ Fourier transform infrared (FT-IR) absorption spectroscopy with isotope labelling. Up to 450 K, the FT-IR peak associated with the OH group of the adsorbed ethanol molecule disappeared from the spectrum, which was attributed to a dehydration reaction with a hydrogen atom from the HB sheet, resulting in the formation of an ethyl species. At temperatures above 440 K, the number of BD bonds markedly increased in CD3CH2OH, compared to CH3CD2OH; the temperature dependence of the formation rate of BD bonds was similar to that of the dehydration reaction rate of ethanol on HB sheets under steady-state conditions. The rate-determining step of the dehydration of ethanol on HB was thus ascribed to the dehydrogenation of the methyl group of the ethyl species on the HB sheets, followed by the immediate desorption of ethylene. These results show that the catalytic ethanol dehydration process on HB involves the hydrogen atoms of the HB sheets. The obtained mechanistic insights are expected to promote the practical application of HB sheets as catalysts.
RESUMO
Hydrogen boride (HB) sheets are metal-free two-dimensional materials comprising boron and hydrogen in a 1:1 stoichiometric ratio. In spite of the several advancements, the fundamental interactions between HB sheets and discrete molecules remain unclear. Here, we report the adsorption of CO2 and its conversion to CH4 and C2H6 using hydrogen-deficient HB sheets. Although fresh HB sheets did not adsorb CO2, hydrogen-deficient HB sheets reproducibly physisorbed CO2 at 297 K. The adsorption followed the Langmuir model with a saturation coverage of 2.4 × 10-4 mol g-1 and a heat of adsorption of approximately 20 kJ mol-1, which was supported by density functional theory calculations. When heated in a CO2 atmosphere, hydrogen-deficient HB began reacting with CO2 at 423 K. The detection of CH4 and C2H6 as CO2 reaction products in a moist atmosphere indicated that hydrogen-deficient HB promotes C-C coupling and CO2 conversion reactions. Our findings highlight the application potential of HB sheets as catalysts for CO2 conversion.
RESUMO
Hydrogen boride (HB) or hydrogenated borophene sheets are recently realized two-dimensional materials that are composed of only two light elements, boron and hydrogen. However, their catalytic activity has not been experimentally analyzed. Herein, we report the catalytic activity of HB sheets in ethanol reforming. HB sheets catalyze the conversion of ethanol to ethylene and water above 493 K with high selectivity, independent of the contact time, and with an apparent activation energy of 102.8 ± 5.5 kJ/mol. Hence, we identify that HB sheets act as solid-acid catalysts.
RESUMO
Hydrogen boride nanosheets (HB sheets) are facilely synthesized via ion-exchange treatment on magnesium diboride (MgB2) in an acetonitrile solution. Optical absorption and fluorescence spectra of HB sheets indicate that their bandgap energy is 2.8 eV. According to first-principles calculations, optical absorption seen at 2.8 eV is assigned to the electron transition between the σ-bonding states of B and H orbitals. In addition, density functional theory (DFT) calculations suggest the other allowed transition from the σ-bonding state of B and H orbitals to the antibonding state with the gap of 3.8 eV. Significant gaseous H2 release is found to occur only under photoirradiation, which causes the electron transition from the σ-bonding state to the antibonding state even under mild ambient conditions. The amount of H2 released from the irradiated HB sheets is estimated to be 8 wt%, indicating that the sheets have a high H2-storage capacity compared with previously reported metal H2-storage materials.