READ ME File For 'Rationalising catalytic performance using a unique correlation matrix' Dataset DOI: https://doi.org/10.5258/SOTON/D3181 Date that the file was created: July, 2024 ------------------- GENERAL INFORMATION ------------------- ReadMe Author: Maciej G. Walerowski, University of Southampton [https://orcid.org/0009-0006-4763-8169]. Date of data collection: October 2023 - August 2024. Information about geographic location of data collection: Southampton, UK and Diamond Light Source, UK. Related projects: Catal. Sci. Technol., 2024,14, 3853-3863. https://doi.org/10.1039/D4CY00020J. -------------------------- SHARING/ACCESS INFORMATION -------------------------- Licenses/restrictions placed on the data, or limitations of reuse: CC BY - This license enables reusers to distribute, remix, adapt, and build upon the material in any medium or format, so long as attribution is given to the creator. The license allows for commercial use. Recommended citation for the data: M. G. Walerowski, S. Kyrimis, V. Hewitt, L. Armstrong & R. Raja, Data in support of 'Rationalising catalytic performance using a unique correlation matrix', University of Southampton, 2024, https://doi.org/10.5258/SOTON/D3181. This dataset supports the publication: Rationalising catalytic performance using a unique correlation matrix. AUTHORS: Maciej G. Walerowski, Stylianos Kyrimis, Victoria Hewitt, Lindsay-Marie Armstrong & Robert Raja. TITLE: Rationalising catalytic performance using a unique correlation matrix. JOURNAL: Chemical Communications PAPER DOI IF KNOWN: https://doi.org/10.1039/D4CC03193H Links to other publicly accessible locations of the data: N/A Links/relationships to ancillary or related data sets: N/A -------------------- DATA & FILE OVERVIEW -------------------- This dataset contains: TEM Images > Broken down into four catalysts sets prepared at different conditions e.g different solvent volumes > Each catalyst set then broken down into specific variable e.g 15 mL solvent volume > Each folder contains 10-15 TIFF images of the specific catalyst. XAS Raw Data Files > Broken down into the Cu and Zn K Edge data > The folder contains all the raw XAS data files for all the catalysts in DAT format. XRD Raw Data Files > Broken down into fresh and spent catalysts > The folder contains all the raw XRD data files for all the catalysts in TXT file format. BET Raw Data Files > Broken down into fresh powder, fresh pelletised and spent pelletised catalysts > The folder contains all the raw BET data files for all the catalysts in excel file format. ICP-MS Raw Data which is an excel spreadsheet containing the raw ICP-MS results for all the catalysts. Catalysis Raw Data which is an excel spreadsheet broken down into four tabs for each catalyst set (solvent volume, drying temperature, solvent and Cu:Zn:SAPO-34 ratio). Each tab then has the raw triplicate results for each variable of the condition set (e.g. 15, 30 or 45 mL). -------------------------- METHODOLOGICAL INFORMATION -------------------------- Description of methods used for collection/generation of data: TEM imaging was performed using a Hitachi HT7700 instrument at an acceleration voltage of 100 kV. The instrument was equipped with a Morada G3 (16 MP) detector for digital imaging. The sample powder was suspended in ethanol and loaded directly onto carbon and formvar coated copper TEM grids. The characterisation was performed at the Biological Imaging Unit at the University Hospital Southampton. The XAS spectra for the Cu and Zn K-edges (8.979 and 9.659 keV respectively) were collected at the general purpose XAS beamline, B18 at the Diamond Light Source (UK) and accessed through the UK Catalysis Hub, block allocation group (BAG, SP34632-1 and SP34632-2). The collimated, white X-ray beam is incident on a Si(111) double crystal monochromator and a Pt-coated focusing mirrors, covering the energy range 6.34 keV to 9.98 keV. The beam size at the sample was approximately 1.0 x 1.0 mm2 (V x H) and the photon flux was ~1011 ph/s (no attenuation). The XAS spectra were collected in transmission mode and the intensity of the incident beam (I0) and the transmitted beam (It) was monitored by ionization chambers (filled with a mixture of He, N2, and Ar). Samples (~30 mg) were diluted with cellulose (~30 mg) before pressing into 13mm diameter pellets. The XAS spectra of each sample were measured at least 2 times in transmission mode at room temperature and merged to improve the signal-to-noise ratio. Zn and Cu metal foil was measured simultaneously for each sample as a reference for energy calibration. XAS data was analyzed using the Demeter software package which includes Athena and Artemis. Powder X-ray diffraction (XRD) characterisation was performed using a Bruker D2 Phaser instrument. Patterns were obtained using Cu Kα radiation (λ = 1.54184 Å) at 30 kV voltage and 10 mA current using a 0.6 mm slit. Patterns were obtained in the 5-60° 2θ range with 0.02° increments and 0.2 s per step. Surface area and porosity characterisation was performed using Micromeritics Tristar II 3020 analyser. N2 was used as the adsorptive, and a liquid N2 bath was utilised. Analysis performed between 0.00 and 0.95 p/p0 (relative pressure). 124 adsorption and 30 desorption points were used to obtain the full physisorption isotherm. BET surface area and pore volume calculated automatically by the Micromeritics Tristar II 3020 software. Samples (~0.15 g) were thoroughly degassed for a minimum of 21 hours using a Micrometrics Vac Prep 062 system by heating them under vacuum at 120°C, with final pressure of ~100 mTorr. Inductively coupled plasma – mass spectrometric (ICP-MS) analysis was performed at the School of Ocean and Earth Science, University of Southampton. Samples (~10 mg) were fully digested in a hot mixture of concentrated HCl (1 mL), HNO3 (1 mL) and HF (0.75 mL) overnight. Digested solutions were subsequently diluted in water and then sub sampled and further diluted with 3% HNO3 to give an approximate dilution of 1 million, and spiked to give Be at 20ppb, and Ru and Re at 5 ppb to act as internal standards. The samples were analysed on a ThermoFisher XSeries2 ICP-MS operating in standard and CCT modes. Calibration was carried out using synthetic standards prepared from Inorganic Venture single element ICP-MS standards and the standards were also spiked to give the same concentration of internal standards as for the samples. Catalysis was performed in a custom built reactor which comprised of hydrogen, argon and carbon dioxide cylinders, three mass flow controllers, laptop computer to control the mass flow controllers and mass spectrometer, heating jacket for the reactor, emergency proportional pressure relief valve, pressure gauge, backpressure regulator, hotplate to heat the backpressure regulator and a mass spectrometer. Temperature, gas flow rate and mass spectrometric calibrations were performed previously to ensure accurate results and quantification. Catalyst powder (~0.4 g) was pelletised at 4 tonnes using a Graseby Specac pellet press for 10 seconds to yield self-supporting discs of 2.5 cm diameter. The discs were then crushed and sieved 5 times between 300 and 500 μm sieves to yield catalyst particles in the 300-500 μm range. The catalyst particles (0.300 g) were then sandwiched between 5 and 17 cm layers of 1 mm borosilicate beads and the reactor placed inside the heating jacket. The catalyst was then reduced in a 60 mL/min H2 flow at 300°C for 2 hours before temperature was reduced to 260°C. Reaction gas mixture of 5.5 Ar, 15 CO2 and 45 H2 mL/min was flown into the reactor and pressure was built up to 40 bars. As soon as the reaction pressure was attained, mass spectrometric analysis was started. The reaction was allowed to proceed for a minimum of 3 hours after which steady state was obtained. Mass spectrometric measurements were taken every ~10 seconds and the results presented are an average over a period of 15 minutes which is approximately equal to 100 analysis points. Argon was used as an internal standard. Each experiment was performed in triplicate, using fresh catalyst on a different day in a randomised order. Standard deviation was calculated between the three repeats to give error in each result. People involved with sample collection, processing, analysis and/or submission: Maciej G. Walerowski, Victoria Hewitt & Stylianos Kyrimis -------------------------- DATA-SPECIFIC INFORMATION -------------------------- Number of variables: Solvent volume (15, 30 or 45 mL), drying temperature (50, 80 or 120oC), solvent (acetone, ethanol or water) and Cu:Zn:SAPO-34 ratio (0.5:0.25:10, 1:0.5:10 or 2:1:10). Variable list, defining any abbreviations, units of measure, codes or symbols used: mL = mililitres, oC = degrees Celsius, Cu = copper, Zn = zinc, SAPO-34 = silicoaluminophosphate-34 TEM = Transmission Electron Microscopy, XAS = X-ray Absorption Spectroscopy, XRD = Powder X-ray Diffraction, ICP-MS = Inductively Coupled Plasma - Mass Spectrometry, BET = Brunauer–Emmett–Teller Specialized formats or other abbreviations used: CZ-S34 = Cu-ZnO/SAPO-34, 9576-003 = Cu-ZnO/SAPO-34 15mL, 9576-005 = Cu-ZnO/SAPO-34 30mL, 9576-007 = Cu-ZnO/SAPO-34 45mL, 9576-013 = Cu-ZnO/SAPO-34 80oC, 9576-016 = Cu-ZnO/SAPO-34 50oC 9576-018 = Cu-ZnO/SAPO-34 Ethanol, 9576-020 = Cu-ZnO/SAPO-34 1:0.5:10, 9576-022 = Cu-ZnO/SAPO-34 0.5:0.25:10 and 9576-026 = Cu-ZnO/SAPO-34 Acetone