--- id: hdl:21.11165/4cat/arp5-s69r title: - Carbonylation catalysis of aryl halides through active-site engineering description: - 'Catalyst characterization (PXRD, DRIFT, CO chemisorption, XPS, STEM) and catalytic testing data for Pd3P/SiO2 (a phosphorus-modified palladium phosphide catalyst, internal code ARNE01) compared against an unmodified Pd/SiO2 reference (ARNE02), for Pd-catalyzed carbonylation reactions of aryl iodides. 31 batch reactor runs span three reaction types: alkoxycarbonylation (27 runs; mainly iodobenzene + ethanol -> ethyl benzoate, exploring reaction time, base, temperature, and substrate/nucleophile scope), phenoxycarbonylation (1 run, phenol nucleophile), and aminocarbonylation (3 runs, aniline nucleophile, 100-140 C). PXRD additionally covers two further Pd3P/SiO2 loading variants (1 wt% and 10 wt% Pd), and STEM additionally covers a recycled/spent Pd3P/SiO2 sample recovered after catalytic testing; STEM method details are documented but no STEM image/data files are included in the deposited dataset.' rdf_type: id: VOC4CAT:0007001 title: heterogeneous catalysis keyword: - Chemistry - Catalysis - Heterogeneous catalysis - Palladium catalyst - Palladium phosphide - Carbonylation - Active-site engineering creator: - name: - Neyyathala, Arjun - name: - Jung, Felix - name: - Barth, Simon - name: - Feldmann, Claus - name: - Grunwaldt, Jan-Dierk - name: - Jevtovik, Ivana - name: - Schunk, Stephan A. - name: - Dolcet, Paolo - name: - Gross, Silvia - name: - Hanf, Schirin publisher: name: - NFDI4Cat Central Data Repository dataset_distribution: - access_URL: - id: https://hdl.handle.net/21.11165/4cat/arp5-s69r title: Repository landing page description: - Repository landing page providing access to the characterization and catalytic testing data files. licence: id: https://creativecommons.org/licenses/by/4.0/ title: CC BY 4.0 other_identifier: - notation: https://hdl.handle.net/21.11165/4cat/arp5-s69r was_generated_by: - id: coremeta4cat:CHAR_arp5-s69r_COChemisorption title: - CO chemisorption analysis (2 catalysts) description: - Pulse CO chemisorption at room temperature (25 C) for Pd3P/SiO2 and Pd/SiO2 (2 replicate runs each), used to determine active surface Pd site density / dispersion by comparing CO uptake between the phosphide and the unmodified reference catalyst. carried_out_by: - id: coremeta4cat:DEV_arp5-s69r_COChemisorption title: Pulse chemisorption analyser description: Instrument model not specified in the source dataset files. evaluated_entity: - id: coremeta4cat:CAT_arp5-s69r_Pd3P_SiO2_5wt title: Pd3P/SiO2 (5 wt% Pd, ARNE01) description: See CatalyticReaction files for full detail. - id: coremeta4cat:CAT_arp5-s69r_Pd_SiO2_5wt title: Pd/SiO2 (5 wt% Pd, ARNE02) description: See CatalyticReaction files for full detail. realized_plan: id: coremeta4cat:CHAR_arp5-s69r_COChemisorption_method title: Pulse CO chemisorption method description: CO pulses at room temperature; peak areas integrated to determine total CO uptake. other_identifier: - notation: https://hdl.handle.net/21.11165/4cat/arp5-s69r activity_designator: Characterization - id: coremeta4cat:CHAR_arp5-s69r_DRIFT title: - DRIFT CO-adsorption spectroscopy (2 catalysts, 2 temperatures) description: - 'Diffuse reflectance infrared Fourier transform spectroscopy of CO adsorbed on Pd3P/SiO2 and Pd/SiO2, at 30 C and 100 C (4 spectra total). Atmosphere: 4000 ppm CO, balance Ar, 50 mL/min flow; Ar flush between measurements. Sample: 50 mg, 100-200 micron sieve fraction, in a Harrick in-situ cell with CaF2 windows.' carried_out_by: - id: coremeta4cat:DEV_arp5-s69r_DRIFT title: VERTEX 70 FTIR spectrometer (Bruker) description: VERTEX 70 FTIR spectrometer (Bruker) equipped with Praying Mantis diffuse reflection optics (Harrick) and a liquid-nitrogen-cooled mercury cadmium telluride (MCT) detector. evaluated_entity: - id: coremeta4cat:CAT_arp5-s69r_Pd3P_SiO2_5wt title: Pd3P/SiO2 (5 wt% Pd, ARNE01) description: See CatalyticReaction files for full detail. - id: coremeta4cat:CAT_arp5-s69r_Pd_SiO2_5wt title: Pd/SiO2 (5 wt% Pd, ARNE02) description: See CatalyticReaction files for full detail. realized_plan: id: coremeta4cat:CHAR_arp5-s69r_DRIFT_method title: CO-adsorption DRIFT method description: Reflectance mode; scanner velocity 20 kHz; aperture 6 mm; MIR source, KBr beamsplitter. other_identifier: - notation: https://hdl.handle.net/21.11165/4cat/arp5-s69r rdf_type: id: CHMO:0000645 title: diffuse reflectance infrared Fourier transform spectroscopy activity_designator: Characterization - id: coremeta4cat:CHAR_arp5-s69r_PXRD title: - Powder XRD phase analysis (4 catalysts) description: - Powder X-ray diffraction for phase identification of Pd/SiO2 (5 wt%, ARNE01/ICSD 85525=Pd3P phase reference, ARNE02/ICSD 52251=Pd phase reference) and two further Pd3P/SiO2 loading variants (1 wt% and 10 wt%), transmission geometry, 2theta 2-90 degrees, ~80 min total measurement per sample. carried_out_by: - id: coremeta4cat:DEV_arp5-s69r_PXRD title: Stoe STADI-MP diffractometer description: Stoe STADI-MP powder diffractometer, Cu X-ray source (lambda=1.54178 A), Ge monochromator. evaluated_entity: - id: coremeta4cat:CAT_arp5-s69r_Pd3P_SiO2_5wt title: Pd3P/SiO2 (5 wt% Pd, ARNE01) description: See CatalyticReaction files for full detail. - id: coremeta4cat:CAT_arp5-s69r_Pd_SiO2_5wt title: Pd/SiO2 (5 wt% Pd, ARNE02) description: See CatalyticReaction files for full detail. - id: coremeta4cat:CAT_arp5-s69r_Pd3P_SiO2_1wt title: Pd3P/SiO2 (1 wt% Pd) description: Lower-loading Pd3P/SiO2 variant, PXRD-only sample. - id: coremeta4cat:CAT_arp5-s69r_Pd3P_SiO2_10wt title: Pd3P/SiO2 (10 wt% Pd) description: Higher-loading Pd3P/SiO2 variant, PXRD-only sample. realized_plan: id: coremeta4cat:CHAR_arp5-s69r_PXRD_method title: Powder XRD measurement method description: Transmission geometry, air atmosphere, ambient temperature; software INSTPAR. other_identifier: - notation: https://hdl.handle.net/21.11165/4cat/arp5-s69r rdf_type: id: CHMO:0000158 title: powder X-ray diffraction activity_designator: Characterization - id: coremeta4cat:CHAR_arp5-s69r_STEM title: - STEM/TEM imaging and EDX mapping (3 catalyst samples) description: - 'Transmission electron microscopy (HRTEM), scanning TEM (HAADF-STEM), and STEM-EDX elemental mapping of Pd3P/SiO2 (ARNE01), Pd/SiO2 (ARNE02), and a recycled/spent Pd3P/SiO2 sample recovered after catalytic testing (ARNE03), for particle size distribution, chemical composition, and crystal structure. Note: STEM-Meta-2.txt documents the method in detail but no image/data files for this technique are included in the deposited dataset.' carried_out_by: - id: coremeta4cat:DEV_arp5-s69r_STEM title: FEI Osiris ChemiSTEM description: FEI/Thermo Fisher Osiris ChemiSTEM, combined TEM and STEM with ChemiSTEM EDX detector, Schottky field emission gun, 200 kV high tension, magnification 160-800 kx. evaluated_entity: - id: coremeta4cat:CAT_arp5-s69r_Pd3P_SiO2_5wt title: Pd3P/SiO2 (5 wt% Pd, ARNE01) description: See CatalyticReaction files for full detail. - id: coremeta4cat:CAT_arp5-s69r_Pd_SiO2_5wt title: Pd/SiO2 (5 wt% Pd, ARNE02) description: See CatalyticReaction files for full detail. - id: coremeta4cat:CAT_arp5-s69r_Pd3P_SiO2_5wt_recycled title: Pd3P/SiO2 (5 wt% Pd, recycled, ARNE03) description: Spent Pd3P/SiO2 catalyst recovered after catalytic testing, examined by STEM for post-reaction stability. realized_plan: id: coremeta4cat:CHAR_arp5-s69r_STEM_method title: STEM/TEM imaging and EDX mapping method description: HRTEM (Digital Micrograph/Gatan) and HAADF-STEM/STEM-EDXS (TEM Imaging and Microscopy/FEI, Esprit/Bruker); Cliff-Lorimer quantification for EDXS. other_identifier: - notation: https://hdl.handle.net/21.11165/4cat/arp5-s69r rdf_type: id: VOC4CAT:0000078 title: transmission electron microscopy activity_designator: Characterization - id: coremeta4cat:CHAR_arp5-s69r_XPS title: - X-ray photoelectron spectroscopy (2 catalysts, Pd 3d and P 2p) description: - XPS binding energy scans of the Pd 3d core level for Pd/SiO2 and Pd3P/SiO2, and the P 2p core level for Pd3P/SiO2, to compare Pd electronic structure/oxidation state between the phosphide and the unmodified reference catalyst. carried_out_by: - id: coremeta4cat:DEV_arp5-s69r_XPS title: XPS spectrometer description: Instrument model not specified in the source dataset files. evaluated_entity: - id: coremeta4cat:CAT_arp5-s69r_Pd3P_SiO2_5wt title: Pd3P/SiO2 (5 wt% Pd, ARNE01) description: See CatalyticReaction files for full detail. - id: coremeta4cat:CAT_arp5-s69r_Pd_SiO2_5wt title: Pd/SiO2 (5 wt% Pd, ARNE02) description: See CatalyticReaction files for full detail. realized_plan: id: coremeta4cat:CHAR_arp5-s69r_XPS_method title: XPS core-level measurement method description: Pd 3d scans for both catalysts; P 2p scan additionally for Pd3P/SiO2. other_identifier: - notation: https://hdl.handle.net/21.11165/4cat/arp5-s69r rdf_type: id: CHMO:0000404 title: X-ray photoelectron spectroscopy activity_designator: Characterization is_about_activity: - id: coremeta4cat:REAC_arp5-s69r_Aminocarbonylation reaction_name: - Pd-catalyzed aminocarbonylation of iodobenzene title: - Aminocarbonylation of iodobenzene over Pd3P/SiO2 (3 runs) description: - Pd-catalyzed aminocarbonylation of iodobenzene with aniline as the nucleophile (in toluene, triethylamine base) to form benzanilide, over Pd3P/SiO2. 3 runs at 100, 120, and 140 C (5 h, CO 10 bar); yield/conversion increased with temperature from 10% to 78%. rdf_type: id: VOC4CAT:0000247 title: carbonylation catalyst_type: - heterogeneous_catalysis catalyst_form: - supported used_catalyst: - id: coremeta4cat:CAT_arp5-s69r_Pd3P_SiO2_5wt title: Pd3P/SiO2 (5 wt% Pd, internal code ARNE01) description: Palladium phosphide (Pd3P) nanoparticles supported on silica, 5 wt% Pd, 0.5 mol% metal loading. has_physical_state: SOLID has_quantitative_attribute: - value: 5.0 has_quantity_type: http://qudt.org/vocab/quantitykind/MassFraction unit: https://qudt.org/vocab/unit/PERCENT description: Pd loading (Overview Reaction Description-2.txt) - value: 0.01 has_quantity_type: http://qudt.org/vocab/quantitykind/Mass unit: https://qudt.org/vocab/unit/GM description: Catalyst mass used per batch test used_reactant: - id: coremeta4cat:REAC_arp5-s69r_CO title: carbon monoxide rdf_type: id: CHEBI:17245 title: carbon monoxide - id: coremeta4cat:REAC_arp5-s69r_Amino_iodobenzene title: iodobenzene - id: coremeta4cat:REAC_arp5-s69r_Amino_aniline title: aniline used_reactor: - id: coremeta4cat:REAC_arp5-s69r_reactor title: Parr 5500 series compact reactor description: Batch autoclave, cylindrical stainless steel reaction chamber (25 mL, 25.4 x 50.8 mm ID), overhead stirrer at 1000 rpm, electric heating. reactor_temperature_range: - min_value: 373.15 max_value: 413.15 has_quantity_type: http://qudt.org/vocab/quantitykind/Temperature unit: https://qudt.org/vocab/unit/K description: 100-140 C across the 3 runs experiment_pressure: - value: 10.0 has_quantity_type: http://qudt.org/vocab/quantitykind/Pressure unit: https://qudt.org/vocab/unit/BAR description: Initial CO pressure, constant across the 3 runs product_identification_method: - id: coremeta4cat:REAC_arp5-s69r_Amino_product_id title: GC-MS product quantification description: Gas chromatography-mass spectrometry with n-decane internal standard. other_identifier: - notation: https://hdl.handle.net/21.11165/4cat/arp5-s69r - id: coremeta4cat:REAC_arp5-s69r_Carbonylation reaction_name: - Pd-catalyzed alkoxycarbonylation of aryl iodides title: - Alkoxycarbonylation of aryl iodides over Pd3P/SiO2 and Pd/SiO2 (27 runs) description: - Pd-catalyzed alkoxycarbonylation (CO insertion + alcohol trapping) of aryl iodides to form aryl esters, mainly iodobenzene + ethanol -> ethyl benzoate. 24 runs used Pd3P/SiO2 (ARNE01), exploring reaction time (5 min - 3 h, series A), base screening (triethylamine, sodium acetate, potassium hydroxide, potassium carbonate, or no base, series B), temperature-time kinetics grid (60-80 C x 0.5-1 h, series k), and substrate/nucleophile scope (methanol, isopropanol, and aryl iodide substrates bromoiodobenzene/iodotoluene/iodoanisole, series S1-S5). 3 further runs (series C) repeated the time-course on Pd/SiO2 (ARNE02, P-free reference) for comparison. Conversion/yield ranged 7-100% across all 27 runs. Batch reactor, CO 6 bar, ethanol solvent (except S1 methanol, S2 isopropanol). rdf_type: id: VOC4CAT:0000247 title: carbonylation catalyst_type: - heterogeneous_catalysis catalyst_form: - supported used_catalyst: - id: coremeta4cat:CAT_arp5-s69r_Pd3P_SiO2_5wt title: Pd3P/SiO2 (5 wt% Pd, internal code ARNE01) description: Palladium phosphide (Pd3P) nanoparticles supported on silica, 5 wt% Pd, 0.5 mol% metal loading. has_physical_state: SOLID has_quantitative_attribute: - value: 5.0 has_quantity_type: http://qudt.org/vocab/quantitykind/MassFraction unit: https://qudt.org/vocab/unit/PERCENT description: Pd loading (Overview Reaction Description-2.txt) - value: 0.01 has_quantity_type: http://qudt.org/vocab/quantitykind/Mass unit: https://qudt.org/vocab/unit/GM description: Catalyst mass used per batch test - id: coremeta4cat:CAT_arp5-s69r_Pd_SiO2_5wt title: Pd/SiO2 (5 wt% Pd, internal code ARNE02) description: Unmodified (phosphorus-free) palladium nanoparticles supported on silica, 5 wt% Pd, 0.5 mol% metal loading -- reference catalyst for comparison against the Pd3P phosphide. has_physical_state: SOLID has_quantitative_attribute: - value: 5.0 has_quantity_type: http://qudt.org/vocab/quantitykind/MassFraction unit: https://qudt.org/vocab/unit/PERCENT description: Pd loading (Overview Reaction Description-2.txt) - value: 0.01 has_quantity_type: http://qudt.org/vocab/quantitykind/Mass unit: https://qudt.org/vocab/unit/GM description: Catalyst mass used per batch test used_reactant: - id: coremeta4cat:REAC_arp5-s69r_CO title: carbon monoxide rdf_type: id: CHEBI:17245 title: carbon monoxide - id: coremeta4cat:REAC_arp5-s69r_Carbonylation_substrate title: aryl iodide substrate description: Iodobenzene in most runs; bromoiodobenzene (S3), iodotoluene (S4), and iodoanisole (S5) in the substrate-scope runs. - id: coremeta4cat:REAC_arp5-s69r_Carbonylation_alcohol title: alcohol nucleophile description: Ethanol in most runs (also the reaction solvent); methanol (S1) and isopropanol (S2) in the nucleophile-scope runs. - id: coremeta4cat:REAC_arp5-s69r_Carbonylation_base title: base description: Triethylamine in most runs; sodium acetate, potassium hydroxide, potassium carbonate, or no base in the base-screening runs (series B). used_reactor: - id: coremeta4cat:REAC_arp5-s69r_reactor title: Parr 5500 series compact reactor description: Batch autoclave, cylindrical stainless steel reaction chamber (25 mL, 25.4 x 50.8 mm ID), overhead stirrer at 1000 rpm, electric heating. reactor_temperature_range: - min_value: 333.15 max_value: 373.15 has_quantity_type: http://qudt.org/vocab/quantitykind/Temperature unit: https://qudt.org/vocab/unit/K description: 60-100 C across the 27 runs experiment_pressure: - value: 6.0 has_quantity_type: http://qudt.org/vocab/quantitykind/Pressure unit: https://qudt.org/vocab/unit/BAR description: Initial CO pressure, constant across all 27 runs product_identification_method: - id: coremeta4cat:REAC_arp5-s69r_Carbonylation_product_id title: GC-MS product quantification description: Gas chromatography-mass spectrometry with n-decane internal standard; conversion/yield/selectivity computed from GC-MS peak areas. other_identifier: - notation: https://hdl.handle.net/21.11165/4cat/arp5-s69r - id: coremeta4cat:REAC_arp5-s69r_Phenoxycarbonylation reaction_name: - Pd-catalyzed phenoxycarbonylation of iodobenzene title: - Phenoxycarbonylation of iodobenzene over Pd3P/SiO2 (1 run) description: - 'Pd-catalyzed phenoxycarbonylation of iodobenzene with phenol as the nucleophile (in toluene, triethylamine base) to form phenyl benzoate, over Pd3P/SiO2. Single run: 100 C, 7 h, CO 6 bar, yield/conversion 30%.' rdf_type: id: VOC4CAT:0000247 title: carbonylation catalyst_type: - heterogeneous_catalysis catalyst_form: - supported used_catalyst: - id: coremeta4cat:CAT_arp5-s69r_Pd3P_SiO2_5wt title: Pd3P/SiO2 (5 wt% Pd, internal code ARNE01) description: Palladium phosphide (Pd3P) nanoparticles supported on silica, 5 wt% Pd, 0.5 mol% metal loading. has_physical_state: SOLID has_quantitative_attribute: - value: 5.0 has_quantity_type: http://qudt.org/vocab/quantitykind/MassFraction unit: https://qudt.org/vocab/unit/PERCENT description: Pd loading (Overview Reaction Description-2.txt) - value: 0.01 has_quantity_type: http://qudt.org/vocab/quantitykind/Mass unit: https://qudt.org/vocab/unit/GM description: Catalyst mass used per batch test used_reactant: - id: coremeta4cat:REAC_arp5-s69r_CO title: carbon monoxide rdf_type: id: CHEBI:17245 title: carbon monoxide - id: coremeta4cat:REAC_arp5-s69r_Phenoxy_iodobenzene title: iodobenzene - id: coremeta4cat:REAC_arp5-s69r_Phenoxy_phenol title: phenol used_reactor: - id: coremeta4cat:REAC_arp5-s69r_reactor title: Parr 5500 series compact reactor description: Batch autoclave, cylindrical stainless steel reaction chamber (25 mL, 25.4 x 50.8 mm ID), overhead stirrer at 1000 rpm, electric heating. reactor_temperature_range: - min_value: 373.15 max_value: 373.15 has_quantity_type: http://qudt.org/vocab/quantitykind/Temperature unit: https://qudt.org/vocab/unit/K description: 100 C, single run experiment_pressure: - value: 6.0 has_quantity_type: http://qudt.org/vocab/quantitykind/Pressure unit: https://qudt.org/vocab/unit/BAR description: Initial CO pressure product_identification_method: - id: coremeta4cat:REAC_arp5-s69r_Phenoxy_product_id title: GC-MS product quantification description: Gas chromatography-mass spectrometry with n-decane internal standard. other_identifier: - notation: https://hdl.handle.net/21.11165/4cat/arp5-s69r is_about_entity: - id: coremeta4cat:CAT_arp5-s69r_all title: Pd3P/SiO2 and Pd/SiO2 catalyst samples description: Palladium phosphide (Pd3P) and unmodified palladium catalysts supported on silica (5 wt% Pd, plus 1 and 10 wt% Pd3P loading variants characterized by PXRD only, and a recycled/spent Pd3P/SiO2 sample characterized by STEM only). See used_catalyst under is_about_activity and evaluated_entity under was_generated_by above for per-sample detail.