Controlled laser-induced dehydrogenation of free-standing graphane probed by pump–probe X-ray photoemission

The effects of optical excitation on fully hydrogenated free-standing nanoporous graphene have been characterized by pump–probe X-ray photoemission spectroscopy. Hydrogenated graphene, known as graphane, is characterized by a sp3 hybridization, which induces a sp3 component in the C 1s core level whose intensity can be used to monitor the hydrogen content. Under optical excitation we observe a partial dehydrogenation of graphane, which we attribute to local laser- induced heating; such result allows us to estimate the thermal conductivity of the material, for which we found an upper limit of 0.2 W/(m K), four orders of magnitude smaller than that of graphene. Such stark difference, combined with the possibility of dehydrogenating the graphane substrate via laser exposure, may be exploited to engineer nanostructured heat conduction channels in organic and hybrid organic–inorganic devices. We then explored the sub-nanosecond dynamics of the C 1s core level, which displays a kinetic energy shift and a peak broadening with two different decay constants, 210 ps and 130 ps, respectively. We assign the former to surface photovoltage, and the latter to transient lattice heating

Tuning the electronic response of metallic graphene by potassium doping

: Electron doping of graphene has been extensively studied on graphene-supported surfaces, where the metallicity is influenced by the substrate. Herewith we propose potassium adsorption on free-standing nanoporous graphene, thus eluding any effect due to the substrate. We monitor the electron migration in the π* downward-shifted conduction band. In this rigid band shift, we correlate the spectral density of the π* state in the upper Dirac cone with the associated plasmon, blue-shifted with increasing K dose, as deduced by electron energy loss spectroscopy. These results are confirmed by the Dirac plasmon activated by the C 1s emitted electrons, thanks to spatially resolved photoemission. This crosscheck constitutes a reference on the correlation between the electronic π* states in the conduction band and the Dirac plasmon evolution upon in situ electron doping of fully free-standing graphene

MoS2 photoelectrodes for hydrogen production: Tuning the S-vacancy content in highly homogeneous ultrathin nanocrystals

Tuning the electrocatalytic properties of MoS2 layers can be achieved through different paths, such as reducing their thickness, creating edges in the MoS2 flakes, and introducing S-vacancies. We combine these three approaches by growing MoS2 electrodes by using a special salt-assisted chemical vapor deposition (CVD) method. This procedure allows the growth of ultrathin MoS2 nanocrystals (1-3 layers thick and a few nanometers wide), as evidenced by atomic force microscopy and scanning tunneling microscopy. This morphology of the MoS2 layers at the nanoscale induces some specific features in the Raman and photoluminescence spectra compared to exfoliated or microcrystalline MoS2 layers. Moreover, the S-vacancy content in the layers can be tuned during CVD growth by using Ar/H2 mixtures as a carrier gas. Detailed optical microtransmittance and microreflectance spectroscopies, micro-Raman, and X-ray photoelectron spectroscopy measurements with sub-millimeter spatial resolution show that the obtained samples present an excellent homogeneity over areas in the cm2 range. The electrochemical and photoelectrochemical properties of these MoS2 layers were investigated using electrodes with relatively large areas (0.8 cm2). The prepared MoS2 cathodes show outstanding Faradaic efficiencies as well as long-term stability in acidic solutions. In addition, we demonstrate that there is an optimal number of S-vacancies to improve the electrochemical and photoelectrochemical performances of MoS2PID2021-126098OB-I00, PID2020-116619GA-C22, TED2021-131788A-I00, SI3/PJI/2021-0050

Pump-Probe X-ray Photoemission Spectroscopy of Free-Standing Graphane

Free-standing nanoporous graphene was hydrogenated at about 60 at.% H uptake, as determined by the emerging of the sp3 bonding component in the C 1s core level investigated by high-resolution X-ray photoelectron spectroscopy (XPS). Fully unsupported graphane was investigated by XPS under optical excitation at 2.4 eV. At a laser fluence of 1.6 mJ/cm2, a partial irreversible dehydrogenation of the graphane was observed, which could be attributed either to the local temperature increase or to a photo-induced softening of the H-to-C stretching mode. The sub-ns dynamics of the energy shift and peak broadening of the C 1s core level revealed two different decay constants: 210 ps and 130 ps, respectively, the former associated with photovoltage dynamics and the latter with thermal heating on a time scale comparable with the synchrotron temporal resolution

Homogeneous spatial distribution of Deuterium chemisorbed on free-standing graphene

Atomic deuterium (D) adsorption on free-standing nanoporous graphene obtained by ultra-high vacuum D2 molecular cracking reveals a homogeneous distribution all over the nanoporous graphene sample, as deduced by ultra-high vacuum Raman spectroscopy combined with core-level photoemission spectroscopy. Raman microscopy unveils the presence of bonding distortion, from the signal associated to the planar sp2 configuration of graphene toward the sp3 tetrahedral structure of graphane. The establishment of D-C sp3 hybrid bonds is also clearly determined by high-resolution X-ray photoelectron spectroscopy and spatially correlated to the Auger spectroscopy signal. This work shows that the low-energy molecular cracking of D2 in an ultra-high vacuum is an efficient strategy for obtaining high-quality semiconducting graphane with homogeneous uptake of deuterium atoms, as confirmed by this combined optical and electronic spectro-microscopy study wholly carried out in ultra-high vacuum conditions

Dielectric response and excitations of hydrogenated free-standing graphene

The conversion of semimetallic suspended graphene (Gr) to a large-gap semiconducting phase is here realized by controlled adsorption of atomic hydrogen (deuterium) on free-standing nanoporous Gr veils. This approach allows to achieve a very clean and neat adsorption, overcoming any spurious influence associated to the presence of substrates. The effects of local rehybridization from sp2 to sp3 chemical bonding are investigated by combining X-ray photoelectron spectroscopy and high-resolution electron energy-loss spectroscopy (HREELS) with ab-initio based modelling. We find that the hydrogen adatoms on the C sites induce a stretching frequency, clearly identified in the vibrational spectra thanks to the use of the D isotope. Overall, the results are compatible with the predicted fingerprints of adsorption on both sides of Gr corresponding to the graphane configuration. Moreover, HREELS of the deuterated samples shows a sizeable opening of the optical band gap, i.e. 3.25 eV, consistent with the modified spectral density observed in the valence band photoemission. The results are in agreement with ab-initio calculations by GW and Bethe–Salpeter equation approaches, predicting a large quasiparticle gap opening and huge exciton binding energy