READ ME FILE For ‘Dual-Site-Mediated Hydrogenation Catalysis on Pd/NiO: Selective Biomass Transformation and Maintenance of Catalytic Activity at Low Pd Loading'
Dataset DOI: https://doi.org/10.5258/SOTON/D1346
ReadMe Author: Peter Wells, University of Southampton
This dataset supports the publication: Dual-Site-Mediated Hydrogenation Catalysis on Pd/NiO: Selective Biomass Transformation and Maintenance of Catalytic Activity at Low Pd Loading' 
Sebastiano Campisi, Carine E. Chan-Thaw, Lidia E. Chinchilla, Arunabhiram Chutia, Gian-luigi A. Botton,  Khaled. M. H. Mohammed, Nikolaos Dimitratos, Peter P. Wells and Alberto Villa
This paper demonstrates the ability of Pd/NiO to direct the selectivity of furfural hydrogenation and maintain performance at low Pd loading by a unique dual-site mechanism
ACS Catalysis
https://doi.org/10.1021/acscatal.0c00414

This dataset contains:
Data supporting figures in the main text and ESI.

The figures are as follows:
___________________________________________________________________________________________________________________________________________________________________
Figure 1: Representative low magnification STEM-HAADF images of Pd-NiO catalyst. (a-d) Montage of HAADF image of Pd particles showing the corresponding EELS elemental maps and RGB reconstructed overlay maps [Green Pd: Pink Ni].	 
Figure 2:High-resolution STEM-HAADF images of 1 wt% Pd/NiO catalyst showing a crystalline particle (a) and sub na-nometer species of Pd distributed across the support (b).
Figure 5. a) HAADF Signal, b) HAADF signal f physical mixture of 1 wt% Pd/TiO2 and NiO after reaction.
Figure S6. High resolution STEM-HAADF images of 1 wt% Pd/NiO catalyst showing a crystalline particle (a) and sub nanometer species of Pd distributed across the support (b). Results of EELS-SI measurement, showing the HAADF image (c) and artificially colored overlay of Pd (green) and NiO (pink) maps (d). Bottom are independent components spectra and their corresponding distribution determined through machine learning methods implemented in Hyperspy.

Images are .png. Data is in .emi, .ser and .DM3 file format to be opened in appropriate microscopy software.
____________________________________________________________________________________________________________________________________________________________________
Figure 3. CO adsorption FTIR studies for Pd/NiO (black line) and Pd/TiO2 (red line). Peaks assigned in blue are present in both catalysts with those is red and black assigned sole-ly to Pd/NiO and Pd/TiO2 respectively.
Figure 7. Pd K edge XANES of 1% Pd/NiO before and after reaction and a reference Pd foil.
Figure 8. k2 weighted Fourier transform EXAFS data with simulat-ed fit for (a) the fresh Pd/NiO and (b) the used Pd/NiO.

Data is in .opj file format to be opened in origin software.

____________________________________________________________________________________________________________________________________________________________________
Figure 4. The optimised structures of furfural adsorbed on (a) Pd(111), (b) NiO(110), (c) TiO2(111) and (d) Pd16/NiO(110) surfaces. For clarity, the furfural molecule and the first two layers of the surfaces are shown as ball and stick and lower layers are shown in the CPK format.
Figure S7. Optimized geometries of perpendicular configurations of furfural on (a) top of Pd atom (Pdtop), (b) bridge between to Pd-atoms (Pdbdg), and (c) hollow site in-between three Pd-atoms (Pdhollow). The optimized geometries of parallel configurations of furfural on Pd(111) (d) Conf.1, (e) Conf.2 and (f) Conf.3.
Figure S8. Optimized geometries of (a) NiO_conf1, (b) NiO_conf2, (c) NiO_conf3, (d) NiO_conf4, (e) NiO_conf5, (f) NiO_conf6, (g) NiO_conf7, (h) NiO_conf8, (i) NiO_conf9, (j) NiO_conf10, (k) NiO_conf11, (l) NiO_conf12, (m) NiO_conf13, (n) NiO_conf14, (o) NiO_conf15, (p) NiO_conf16, (q) NiO_conf17, (r) NiO_conf18, (s) NiO_conf19.
Figure S9. Optimized geometries of (a) TiO2_conf1, (b) TiO2_conf2, (c) TiO2_conf3, (d) TiO2_conf4, (e) TiO2_conf5, (f) TiO2_conf6, (g) TiO2_conf7, (h) TiO2_conf8, (i) TiO2_conf9, and (j) TiO2_conf10.
Figure S10. Optimised structures of (a) furfural parallel (Ead = -1.946 eV), (b) furfural on top of Pd-atom (Ead = -0.396 eV), (c) furfural in between two Pd-atoms (Ead = -0.964 eV), (d) furfural in the HCP (Ead = -1.017 eV) site of Pd16-NiO(110) systems.
Figure S11. The energy barrier for the for the forward and reverse reaction of H2 dissociation.

Data is in a compressed archive .zip containing .cif and .vasp files to be opened in Materials Studio software.
__________________________________________________________________________________________________________________________________________________________________

Figure 6. Reusability study for 1 wt% Pd/NiO detailing changes to conversion and selectivity over 8 cycles, reaction time 5h. Recycling experiments were performed by reusing the catalyst in the next run without any additional pre-treatment.

Data is in .opj file format to be opened in origin software.
___________________________________________________________________________________________________________________________________________________________________

Figure 7.Pd K edge XANES of 1% Pd/NiO before and after reaction and a reference Pd foil.
Figure 8. k2 weighted Fourier transform EXAFS data with simulat-ed fit for (a) the fresh Pd/NiO and (b) the used Pd/NiO.
This data is in .prj file format to be opened in Arthena and Artemis software package.
____________________________________________________________________________________________________________________________________________________________________

Figure S1. XRD patterns of NiO. 
Data is in .opju file format to be opened in origin software.
_____________________________________________________________________________________________________________________________________________________________________

Figure S2. Pd 3d XPS data for (a) Pd/NiO, (b) Pd/TiO2 and (c) Ni2p3/2 XPS data for NiO.
Image is .png.Data is in .opj file format to be opened in origin software. 
_____________________________________________________________________________________________________________________________________________________________________

Figure S3. Reaction profile for 1 wt% Pd/TiO2 and  b) 1 wt% Pd/NiO.
Data is in .opj file format to be opened in origin software.
______________________________________________________________________________________________________________________________________________________________________

Figure S4. Selectivity vs conversion for a) 1 wt% Pd/TiO2 and  b) 1 wt% Pd/NiO.
Data is in .opj file format to be opened in origin software.
_______________________________________________________________________________________________________________________________________________________________________

Figure S5. Particle size distribution for a) 1 wt% Pd/TiO2 and b) 1wt% Pd/NiO.
Data is in .opju file format to be opened in origin software.
_______________________________________________________________________________________________________________________________________________________________________

Figure S12. Particle size distribution for a) 0.1 wt% Pd/TiO2 and b) 0.1 wt% Pd/NiO.
Data is in .opju file format to be opened in origin software.
_______________________________________________________________________________________________________________________________________________________________________



Date of data collection: October 2016 – February 2020
Information about geographical location of data collection: University of Southampton, U.K.; Università degli Studi di Milano, Italy; McMaster University, Canada; University of Lincoln, U.K.
Dataset available under a CC-BY licence
Relations to funding: EPSRC: EP/K014668/1, EP/K014706/1, EP/I019693/1, EP/K014714/1, EP/K014854/1, EP/R011710/1
STFC: ST/R002754/1

Publisher: University of Southampton, U.K. 
Date: April, 2020