Adsorption and decomposition of γ-butyrolactone on Pd(111) and Pt(111)

Effects of Ring Structure on the Reaction Pathways of Cyclic Esters and Ethers on Pd(111)

“…It is important to note, however, that the computed GBL desorption energy is lower than that expected from a 250 K desorption state. The reasons for the quantitative differences are not clear, since experimental HREEL spectra are consistent with GBL being relatively unperturbed from its liquid state as in the computed structure [11]. The computed GBL adsorption energy is also in line with those calculated for other saturated esters [20].…”

“…The molecular desorption state of 25HF was observed to be close to 300 K, consistent with a desorption energy of roughly 0.8 eV, in good agreement with the DFT results reported here. In contrast, the saturated lactone GBL was found to adsorb through the ester function, with weaker adsorption indicated by desorption of the molecular state near 250 K [11]. It is important to note, however, that the computed GBL desorption energy is lower than that expected from a 250 K desorption state.…”

“…Interestingly, the ring-opening reaction of the saturated lactone GBL differs significantly from 25HF [11]. Although GBL is bound more weakly, the decomposition temperature is actually lower than for 25HF.…”

“…Previous studies have focused on the thermal chemistry of the probe molecule furan on Pd(111) [5][6][7][8][9]. More recent investigations have considered the thermal chemistry of 2(5H)-furanone (25HF) [10] and c-butyrolactone (GBL) [11] on the same surface. While not a five-membered ring, 1-epoxy-3-butene (EpB) is a C 4 cyclic ether that allows an exploration of ring strain, and its chemistry has likewise recently been studied on Pd(111) [12].…”

ChemInform Abstract: Reaction Pathways of Biomass‐Derived Oxygenates over Metals and Carbides: From Model Surfaces to Supported Catalysts

“…Catalytic surfaces Te chniques 2(5 H)-furanoneP d(111)T PD, [84] HREELS [84] 2(5 H)-furanoneP t(111)T PD, [84] HREELS [84] 2-methyl-1propanol Rh(111)T PD, [85] HREELS [85] 2-methyl-1propanal Rh(111)T PD, [85] HREELS [85] 2-methyl-2propanol Rh(111)T PD, [85] HREELS [85] 2,2-dimethyl-1propanol Rh(111)T PD, [85] HREELS [85] 2,2-dimethyl-1propanal Rh(111)T PD, [85] HREELS [85] r-butyrolactone Pd(111)T PD, [86] HREELS [86] r-butyrolactone Pt(111)T PD, [86] HREELS [86] All reported valuesa re electronic energyo ft he transition stater elative to ethylene glycol in vacuum, ac lean Pt(111)o rN i/Pt(111)s lab,a nd excess hydrogen atoms adsorbed on separate slabs. Labels in parentheses correspond to Figure 1.…”