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The activation of the C=O bonds in aldehyde In situ FT-IR spectra after the adsorption of acetaldehyde for 30 min followed by desorption at desorption times of 1, 5, 10, 15, and 20 min (from top to bottom) on 0.9%Pt1+Ptn/Cu-CuZrOx (a), and 0.9%Ptn/Cu-CuZrOx (b), with enlarged spectra between 1360 and 1300 cm⁻¹ filled in olive shading (c). The simulated adsorption models are displayed corresponding to the adsorption band labeled in the same color.
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The selective oxidation of glycerol to glyceric acid, an important value-added reaction from polyols, is a typical cascade catalytic process. It is still of great challenge to simultaneously achieve high glycerol activity and glyceric acid selectivity, suffering from either deep oxidation and C-C cleavage or poor oxidation efficiency from glycerald...
Citations
... The investigation into the products of glycerol electrooxidation reaction (GEOR) was carried out (Table 5) [52,53]. These findings collectively highlight the significant potential of carbon derived from glycerol, and effects of insitu phosphorus doping as an excellent support material for electrocatalytic applications. ...
... As shown in Supplementary Fig. 17, these two regions exhibited negative peaks compared with the OCP spectrum, and the regions decreased as the potential increased from 0.3 to 1.1 V RHE , indicating the dehydrogenation of glycerol's primary alcohol group adsorbed on the catalyst surface. The symmetric stretch v(OCO) of twofold carboxylate species appeared at 1400 cm −1 (marked in magenta), consistent with previous reports 29,40,41 . The band at 1533 cm −1 corresponded to v(OCO) in a bridging bidentate configuration (also marked in magenta) involving two Pt sites 40 . ...
... The symmetric stretch v(OCO) of twofold carboxylate species appeared at 1400 cm −1 (marked in magenta), consistent with previous reports 29,40,41 . The band at 1533 cm −1 corresponded to v(OCO) in a bridging bidentate configuration (also marked in magenta) involving two Pt sites 40 . The band centered at 1590 cm −1 corresponded to the (C = O) acyl stretch mode of adsorbed aldehyde species 29 . ...
... The surface hydrogen bonds associated with OH − and glycerol oxidation intermediates concentration were further investigated. The bands around 3236 and 3541 cm −1 were identified as surface OH groups involved in hydrogen bonds on the metal catalyst surface and free OH groups, respectively 40 . The bands in the 3100-3700 cm −1 region increased as the potential increased ( Supplementary Fig. 17) and with an increase in electrolysis time during CE at 0.7 V RHE ( Supplementary Fig. 19) and 1.1 V RHE (Supplementary Fig. 18a). ...
Preventing the deactivation of noble metal-based catalysts due to self-oxidation and poisonous adsorption is a significant challenge in organic electro-oxidation. In this study, we employ a pulsed potential electrolysis strategy for the selective electrocatalytic oxidation of glycerol to glyceric acid over a Pt-based catalyst. In situ Fourier-transform infrared spectroscopy, quasi-in situ X-ray photoelectron spectroscopy, and finite element simulations reveal that the pulsed potential could tailor the catalyst’s oxidation and surface micro-environment. This prevents the overaccumulation of poisoning intermediate species and frees up active sites for the re-adsorption of OH adsorbate and glycerol. The pulsed potential electrolysis strategy results in a higher glyceric acid selectivity (81.8%) than constant-potential electrocatalysis with 0.7 V RHE (37.8%). This work offers an efficient strategy to mitigate the deactivation of noble metal-based electrocatalysts.
... 39,40 OVs can effectively activate molecular oxygen to form reactive oxygen species with upgraded oxygen mobility and reactivity, and further enhance the initiation of C−H bond and the transformation of intermediates. 41,42 Therefore, OV concentration is the crucial structural parameter to evaluate its catalytic activity of CVO materials in selective oxidation, which can be calculated based on the ratio of peak area (O v /(O L + O v + O γ ) and it was summarized in Table 2. The CVO-300 catalyst had the lowest surface OV concentration under lowtemperature heat treatment, while the OV concentration was improved through increasing the calcination temperature as depicted in the CVO-700 catalyst. ...
... Currently, selective oxidation of glycerol is one of the main pathways for glycerol conversion. Among various oxidation products, glyceric acid (GLYA) is sought after for its unique applications [7][8][9][10] . ...
A series of mesoporous Zr@MCM-41 zeolite with different Si/Zr molar ratios were prepared with cetyltrimethylammonium bromide (CTAB) as template. And then Pt nanoparticles were successfully loaded onto the Zr@MCM-41 by colloid-deposition method. These catalysts were evaluated for catalytic oxidation of glycerol to glyceric acid at low-temperature. The results showed that the molar ratios of Si/Zr affected oxidizing of the primary OH group, in turn affects the catalytic activity and selectivity. The Pt/Zr@MCM-41-100 catalyst showed the best catalytic activity with the conversion of glycerol and selectivity for glyceric acid reached 50.7% and 65.0%, respectively. A combination of multi-characterizations by X-ray diffraction (XRD), N 2 adsorption and desorption, Fourier transform infrared spectroscopy (FTIR), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Ultraviolet-visible (UV-vis) spectroscopy. The result confirmed that the catalytic activity of Pt/Zr@MCM-41-100 was related to the support structure, the dispersion of the Pt nanoparticles and the interaction between Pt nanoparticles and the support. Meanwhile, we investigated the stability of Pt/Zr@MCM-41-100 catalyst and analyzed the deactivation reasons by charaterization.
... 1412 1328, 1200, 1110, and 1044 cm À1 on Pt iso /D-TiO 2 . According to previous literatures,46,47 two strong adsorption bands at 1044 and 1100 cm À1 were attributed to primary and secondary ν(C O) of monodentate dissociated glycerol. The bands at 1460 and 1412 cm À1 could be assigned to the methyl symmetric δ as mode (δ[CH 3 ] as ) and asymmetric δ s mode (δ[CH 3 ] s ). ...
We propose to fabricate a bifunctional photocatalyst for cooperative glycerol selective oxidation and H2 evolution. The key role of interface scale (nanometer, subnanometer, or atomic level) on tuning catalysis performance was revealed. Specifically, series Pt/defective TiO2 with tailored interface scale were constructed by loading Pt nanoparticle, cluster, and single atom on VTi‐enriched TiO2. It was uncovered that reducing interface scale could largely improve the visible‐light utilization efficiency, the photoexcited electron–hole separation, and well tuned the band structure. It could also enhance the metal–support interaction and thus adjust the chemical behavior toward reactant molecules. The optimized isolated Pt/defective TiO2 with atomic‐level interface achieved 90.6% glycerol conversion and 87.2% C3 products selectivity, accompanied by 7250.4 μmol g⁻¹ H2 accumulative yield. It also exhibited long‐term stability of 36 h without performance loss. Besides, the dominate active site was identified and the possible reaction mechanism was illustrated combined with Density Functional Theory (DFT) calculation and quasi in situ experiments.
We introduce an innovative in situ infrared diffuse reflection rapid detection system, endowed with a temperature regulation function. This system is adept at conducting rapid infrared spectra scanning as well...
