Deciphering key intermediates

The identification of catalytic intermediates in the conversion of carbon dioxide is vital for improved catalyst design and optimization of structure?reactivity relationships, but remains elusive. Here, we report that intermolecular hydrogen bonding interactions between an epoxy alcohol, water and the catalyst structure are crucial towards the formation of a cyclic carbonate from carbon dioxide. A combination of multiple in situ and ex situ techniques including substrate labelling, kinetic studies, computational analysis, operando infrared spectroscopy and X-ray diffraction was applied to identify and support the structural connectivities of several previously unknown intermediates. An epoxy alcohol?water cluster formed by hydrogen bonding was identified as the initial intermediate able to trap CO2 and an elusive alkyl carbonate anion was also detected. The synergistic spectroscopic and computational analysis shown here offers a unique insight under operando conditions, as well as a useful analytical blueprint for key suggested intermediates in other mechanistically related CO2 conversion processes.

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This dataset derived results are published in:

Manuscript title: Deciphering key intermediates in the transformation of carbon dioxide into heterocyclic products

Journal: Nature Catalysis

PreviewTitleAuthor(s)ProgramCalculation typeMethod(s)Basis SetLinksEnergySolv.Vibr.Orb.
thumbnail.jpeg/NMR_IR/IR/BP86/TBDH_HCO3/Freq FreqGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Single point StructureRBP86--703.846157215; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/TBDH_HCO3/Opt_Freq Opt_FreqGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--704.104642814; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/TBD_CO2/Opt_Freq Opt_FreqGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--627.624870027; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/TBD_CO2/Freq FreqGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Single point StructureRBP86--627.455792855; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/Carbonate_Water_NoAl Carbonate_Water_NoAlGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--456.572117669; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/HCarb2 HCarb2González Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--2027.46112978; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/Product ProductGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--457.083650403; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/Water WaterGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--76.4548910187; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/Linear_Carbonate_Water Linear_Carbonate_WaterGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--2103.94059534; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/CarbH_Eq CarbH_EqGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--2027.44955854; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/Acid AcidGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--457.049412797; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/Carbonate CarbonateGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--2027.46224980; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/Carbonate_Water/HCarb_Water/Frozen FrozenGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--2103.91836151; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/Carbonate_Water/HCarb_Water HCarb_WaterGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--2103.92129351; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/Carbonate_Water Carbonate_WaterGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--2103.93757379; Eh
thumbnail.jpeg/NMR_IR/IR/BP86/HCarb HCarbGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRBP86--2027.46121012; Eh
thumbnail.jpeg/NMR_IR/IR/wB97xD/HCarb_Water HCarb_WaterGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRwB97XD--2103.34214861; Eh
thumbnail.jpeg/NMR_IR/IR/wB97xD/HCarb/Cyclohexane CyclohexaneGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRwB97XD--2026.88457210; Eh
thumbnail.jpeg/NMR_IR/IR/wB97xD/HCarb/B3LYP B3LYPGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRB3LYP--2027.48159170; Eh
thumbnail.jpeg/NMR_IR/IR/wB97xD/HCarb/Free FreeGonzález Fabra, JoanGaussian; 09; EM64L-G09RevD.01Geometry optimization MinimumRwB97XD--456.894721718; Eh
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