This dataset pertains to an extensive study of the electronic structure of CO adsorbed on various active site topologies on cobalt. The following cobalt active site configurations were explored:

Co(0001) (fcc)

Co(0001) (hcp)

Co(11-21) 3f

Co(11-21) B5

Co(100)

Co(110)

Co55/Al2O3 (top)

Co55/Al2O3 (interfacial site)

Co52/Al2O3 (defect site)

Co84/Al2O3 (nanorod)

Co54/TiO2 (cluster)

Co81/TiO2 (nanorod)

For each adsorption site, a density of states and crystal orbital hamilton population analysis was performed by means of the Lobster program. The original electronic structure calculations are performed using VASP. The input and output files for all calculations as well as the Python scripts how these files were parsed are found in this repository.

Antiferromagnetic interactions on geometrically frustrated lattices such as the fcc lattice can result in novel magnetic states and structures. Ba2CoMoO6 is an fcc antiferromagnet ordering at 27 K with magnetic Co2+ ions displaying an unquenched orbital moment. These orbital effects are expected to play a significant role in the magnetic properties. We have produced the series Ba2Co1-xZnxMoO6 where the coupling between sites on the fcc lattice is randomly disrupted by diamagnetic Zn2+. Unexpectedly the net antiferromagnetic interactions become stronger upon dilution reaching a maximum at x = 0.25. We will use two days on GEM to examine the magnetic ordering, and any associated structural distortions and orbital ordering of compositions x = 0, 0.15, 0.25 and 0.5. This will unambiguously show the impact of any orbital-ordering on the bonding and resultant magnetic structure.

Data presented in the graphical figures of our manuscript entitled ‘Evolution of magneto-orbital order upon B-site electron doping in Na1−xCaxMn7O12 quadruple perovskite manganites’ can be access here, in accordance with the EPSRC policy framework on research data. The data are provided in plain text files and in xye format. The file names identify the figure and the colour, symbol, and line of the data, as presented in the main manuscript. Full details of the data collection and analysis are provided in the main manuscript.

We investigate a layer of cobalt tetrapyridyl porphyrins (CoTPyPs) self-assembled on an almost freestanding graphene (GR) sheet supported by Ir(111) with complementary experimental techniques and density functional theory (DFT) ab initio simulations. Beside the metal atoms enclosed within the porphyrin macrocycles, additional Co atoms can be accommodated at the molecular network’s interstice via physical vapor deposition and can bind up to four adjacent molecules. Therefore, such a system presents two metallic sites, both tetra-coordinated to nitrogen atoms. At the same time, a rearrangement of the network occurs depending on the coverage of such additional atoms. The bare CoTPyPs arrange themselves on GR in an almost hexagonal close-packed pattern with alternating orientations. The addition of extra Co atoms causes a dramatic transformation in the network. At full peripheral metal coverage (i.e., one additional Co per CoTPyP), the network drastically changes becoming almost square. Intermediate coverages display different peculiar patterns characterized by unique chiral structures. Importantly, our DFT calculations reveal a remarkable effect on the system’s work function attributed to the presence of these additional metal atoms, despite their extremely small amount even at full coverage (less than 2% of a monolayer with respect to the number of carbon atoms in the GR sheet). Furthermore, we report a different behavior of the two Co sites showing different oxidation states and molecular orbital occupations.

It is of great significance to reveal the influence of small differences in the coordination environments of metal ions in the catalytic active centers on the selectivity of products in the electrocatalytic CO2 reduction reaction (CO2RR). Here, two types of metal–organic frameworks (MOFs) based on square-pyramidal CuO5 and square-planar CuO4 nodes, respectively, are compared in regard to their performances in electrocatalytic CO2RR. The MOF (Cu-DBC, H8DBC = dibenzo-[g,p]chrysene-2,3,6,7,10,11,14,15-octaol) constructed by CuO5 nodes and the catechol-derived ligands exhibit high performance for the electrocatalytic reduction of CO2 to CH4 with a Faradaic efficiency of 56% and a current density of 11.4 mA cm–2 at −1.4 V vs RHE. In comparison, two other MOFs, Cu-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) and Cu-THQ (THQ = tetrahydroxy-1,4-quinone), constructed by CuO4 and catechol-derived ligands, exhibit that CO is the sole reduced product. Theoretical calculations and Cu L-edge adsorption spectroscopy revealed that the energy levels of metal d-orbitals (dz2, dxz, and dyz) in the square-pyramidal CuO5 site are elevated compared to those in the square-planar CuO4 site. As a result, the CuO5 active sites can strongly adsorb *CO intermediates and hence facilitate the hydrogenation of *CO into *CHO, which is beneficial for yielding CH4 instead of CO. This work will be helpful to understand the mechanism of copper-based catalysts for the electrocatalytic reduction of CO2 to hydrocarbons.

This dataset contains plain text files of data plotted in the respective publication, archived in accordance with the EPSRC policy framework on research data. Full details of data collection and analysis are given in the publication.