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The quest to make free-standing monolayer gold has hitherto been limited to free-standing several-atoms-thick layers, or monolayers but confined on or inside another template. Examples are monolayers diffused into double hydroxides1, membranes framed in alloys under electron irradiation2, nano-ribbons suspended in graphene3, quantum dots on hexagonal BN4, monolayers in between SiC wafers and monolayer graphene5, and fragments produced via thermal dewetting on sapphire6. Here, we report the synthesis of free-standing single-atom-thick 2D gold (named goldene) by wet-chemically etching away Ti3C2 from Ti3AuC2, a nano-laminated MAX-phase ceramic initially formed by substituting Si in Ti3SiC2 with Au7. The free-standing goldene layers are revealed by scanning transmission electron microscopy. While ab initio molecular dynamics simulations show that 2D goldene is inherently stable, the experiments reveal a tendency for curling and agglomeration at edges. Prospects for preparing goldene from a series of non-van der Waals Au-intercalated MAX-phases, including developing etching schemes, are also presented.

The design of active and selective co-catalysts constitutes one of the major challenges in developing heterogeneous photocatalysts for energy conversion applications. This work provides a comprehensive insight into thermally induced bottom-up generation and transformation of a series of promising Cu-based co-catalysts. We demonstrate that the volcano-type HER profile as a function of calcination temperature is independent of the type of the Cu precursor but is affected by changes in oxidation state and location of the copper species. Supported by DFT modeling, our data suggest that low temperature (200 °C) do not affect the Cu oxidation state, but induce a gradual, temperature-dependent surface-to-bulk diffusion of Cu, which results in interstitial, tetra-coordinated Cu+ species. The disappearance of Cu from the surface and the introduction of new defect states is associated with a drop in HER performance. This work examines electronic and structural effects that are in control of the photocatalytic activity and can be transferred to other systems for further advancing photocatalysis., Calcination of Cu/TiO2 is detrimental to its photocatalytic HER performance. We relate this to heat-activated Cu diffusion into the TiO2 lattice, which decreases accessibility of the Cu sites on the surface and generates charge recombination centers.

Thermally induced intercalation of noble metals into non-van der Waals ceramic compounds presents a method to produce a new class of layered materials. We recently demonstrated an exchange reaction of Au with A layers of MAX phase carbides with plentiful combinations of A and M elements. Here, we report the first substitution of Al with Au in a Ti2AlN MAX phase nitride at an elevated temperature without destroying the original layered structure. These results bolster the generalization of the Au intercalation for the A elements in MAX phases with diverse combinations of M, A, and X elements. Furthermore, we propose crucial factors to achieve the exchange reaction: there should be a chemical potential for the A element to dissolve in or react with noble metals to intercalate; the noble metals should be inert to the initial metal carbides/nitrides; and it is necessary to choose the reaction temperature that allows balanced interdiffusion of the noble metals and A elements. Funding Agencies|Swedish Research CouncilSwedish Research Council [2017-03909, 642-2013-8020]; Knut and Alice Wallenberg (KAW) FoundationKnut & Alice Wallenberg Foundation; Swedish Foundation for Strategic Research (SSF)Swedish Foundation for Strategic Research [EM16-0004]

Polycrystalline anatase thin films, (001)- and (101)-oriented anatase TiO 2 single crystals and (001)- and (110)-oriented rutile TiO 2 single crystals with various surface treatments were studied by photoelectron spectroscopy to obtain their surface potentials. Regardless of orientations and polymorph, a huge variation of the Fermi level and work function was achieved by varying the surface condition. The most strongly oxidized surfaces are obtained after oxygen plasma treatment with a Fermi level ∼2.6 eV above the valence band maximum and ionization potentials of up to 9.5 eV (work function 7.9 eV). All other treated anatase surfaces exhibit an ionization potential independent of surface condition of 7.96 ± 0.15 eV. The Fermi level positions and the work functions vary by up to 1 eV. The ionization potential of rutile is ∼0.56 eV lower than that of anatase in good agreement with recent band alignment studies.

Correction for ‘Elucidating the formation and active state of Cu co-catalysts for photocatalytic hydrogen evolution’ by Jasmin S. Schubert et al., J. Mater. Chem. A, 2021, DOI: 10.1039/d1ta05561e.

International audience; Facet-engineered anatase TiO2 with NiO nanoparticles heterocontacts were successfully prepared by selective photodeposition of NiO nanoparticles onto the {101} facet of the top-truncated bipyramidal TiO2 anatase nanocrystals coexposed with {001} and {101} facets. The morphology and electronic properties of the resulting 0.1–10 wt % NiO-decorated TiO2 were investigated by X-ray diffraction, high-resolution electron microscopy, N2 sorption analysis, and UV–vis spectroscopy. Furthermore, a careful determination of the energy band alignment diagram was conducted by a model experiment using XPS and UPS to verify charge separation at the interface of the NiO−TiO2 heterostructure. The model experiment was performed by stepwise deposition of NiO onto oriented TiO2 substrates and in-situ photoelectron spectroscopy measurements without breaking vacuum. Core levels showed shifts of 0.58 eV toward lower binding energies, meaning an upward band bending in TiO2 at the NiO–TiO2 interface. Furthermore, 0.1 wt % NiO–TiO2 exhibited 50% higher activities than the pure TiO2 for methylene blue (MB) photodecomposition under UV irradiation. This enhanced photocatalytic activity of NiO–TiO2 nanocomposites was related to the internal electric field developed at the p–n NiO−TiO2 heterojunction, leading to vectorial charge separation. Finally, mechanistic studies conducted in the presence of carrier or radical scavengers revealed that holes dominantly contributed to the photocatalytic reactions in the case of NiO–TiO2 photocatalysts while electrons played the main role in photocatalysis for the pure TiO2 materials.

International audience; NiO/(101)-anatase-TiO2 heterostructure nanoparticles were synthesized by depositing NiO onto the (101) facet of anatase crystals via the supercritical fluid chemical deposition (SFCD) route. Thorough characterization experiments performed by various techniques (XRD, UV-Vis DRS, N2 sorption, HR-TEM, EDX, and XPS) indicate that the SFCD method allowed a good dispersion of NiO onto the TiO2 nanoparticles for NiO amounts below 2 wt%. Compared to pure TiO2, the 0.1–1 wt% NiO–TiO2 nanocomposites showed enhanced photocatalytic properties for methylene blue (MB) and methyl orange (MO) decomposition under UV light irradiation, the 0.25 wt% NiO–TiO2 system leading to the highest efficiencies. The photocatalytic properties were then rationalized in terms of the acidic properties and electronic structures of the NiO–TiO2 nanocomposites. This higher photocatalytic activity was mainly related to the heterocontact at the interface of the NiO–TiO2 crystallites and to the enhanced reaction rates at the NiOx surface.