Glycolic acid (GA) is a promising building block for synthesizing biodegradable materials, which could replace conventional coal-derived and petroleum-derived plastic materials. However, conventional coal-based GA routes are facing severe obstacles in nonrenewable energy consumptions and pollutant emissions. Biomass energy is regarded as a potential contributor to a greener and cleaner development. Herein, we develop and evaluate a novel ethylene glycol (EG) selective oxidation to GA process using renewable biomass energy, which aims to realize the sustainable and cost-effective production of GA based on the highly efficient bimetallic PtMn/MCM-41 nanocatalysts. Compared with other GA production processes, the bio-based EG selective oxidation to GA process has significantly boosted the techno-economic performance (increasing the energy efficiency by 19.7% and the net present value by 121%). Furthermore, the life cycle society−environment assessment also indicates that the performance of fossil energy demand (FED), greenhouse gas (GHG) emissions, and water resource consumption (WRC) in the EG selective oxidation to GA process is superior to that of other coal-based techniques (reducing FED, GHG, and WRC by 881.3, 32.7, and 47.8%, respectively). This study aims to give unambiguous and quantitative results for developing a sustainable and cost-effective bio-based GA production process and provide guidance for other engineering applications of biomass polyhydric alcohols.
Achieving efficient catalytic conversion over a heterogeneous catalyst with excellent resistance against leaching is still a grand challenge for sustainable chemical synthesis in aqueous solution. Herein, we devised a single‐atom Pt1/hydroxyapatite (HAP) catalyst via a simple hydrothermal strategy. Gratifyingly, this robust Pt1/HAP catalyst exhibits remarkable catalytic selectivity and catalyst stability for the selective oxidation of C2–C4 polyols to corresponding primary hydroxy acids. It is found that the Pt−(O−P) linkages with strong electron‐withdrawing function of PO43− (Pt1−OPO43− pair active site) not only realize the activation of the C−H bond, but also destabilize the transition state from adsorbed hydroxy acids toward the C−C cleavage, resulting in the sharply increased selectivity of hydroxy acids. Moreover, the strong PO43−‐coordination effect provides electrostatic stabilization for single‐atom Pt, ensuring the highly efficient catalysis of Pt1/HAP for over 160 hours with superior leaching resistance.
Achieving efficient catalytic conversion over a heterogeneous catalyst with excellent resistance against leaching is still a grand challenge for sustainable chemical synthesis in aqueous solution. Herein, we devised a single‐atom Pt1/hydroxyapatite (HAP) catalyst via a simple hydrothermal strategy. Gratifyingly, this robust Pt1/HAP catalyst exhibits remarkable catalytic selectivity and catalyst stability for the selective oxidation of C2–C4 polyols to corresponding primary hydroxy acids. It is found that the Pt−(O−P) linkages with strong electron‐withdrawing function of PO43− (Pt1−OPO43− pair active site) not only realize the activation of the C−H bond, but also destabilize the transition state from adsorbed hydroxy acids toward the C−C cleavage, resulting in the sharply increased selectivity of hydroxy acids. Moreover, the strong PO43−‐coordination effect provides electrostatic stabilization for single‐atom Pt, ensuring the highly efficient catalysis of Pt1/HAP for over 160 hours with superior leaching resistance.
A systematic study of Au-promoted and unpromoted Pt/MgO/SBA-15 catalyst is developed to separate the promoter effect from electron transfer effect between Au and Pt. Multi-characterizations revealed that Au and Pt metals in these bimetallic catalysts mainly exist in the form of alloy, and the main role of Au is to reduce the size of AuPt alloy nanoparticles, thus enhancing the adsorption and activation of intermediate products. Through the optimization of various factors (including MgO content, Au/Pt molar ratio, reaction temperature and time), the Au 1 Pt 2 /MgO/SBA-15 (0.05) catalyst exhibits excellent catalytic activity and glyceric acid selectivity for the selective oxidation of glycerol. Density functional theory calculation confirmed that the synergistic effect between Pt and Au active sites could facilitate the oxidation of primary hydroxyl group by promoting the activation of C H bond and the oxidation of aldehyde group. The results may give insights on designing effective Pt based bimetallic catalyst for selective oxidation of glycerol.
Achieving efficient catalytic conversion over heterogeneous catalyst with excellent resistance against leaching is still a grand challenge for sustainable chemical synthesis in aqueous solution. Herein, we devised a leaching free atomically dispersed Pt1/hydroxyapatite (HAP) catalyst with unique switchable structure via a simple and green in-situ anchoring strategy. Gratifyingly, this robust Pt1/HAP catalyst exhibits remarkable catalytic selectivity and catalyst stability for the selective oxidation of C2-C4 bio-polyols (e.g., ethylene glycol, propanediol, glycerol and butanediol) to corresponding primary hydroxy acids. X-ray absorption spectroscopy, in-situ Fourier Transform infrared spectroscopy, density functional theory calculation and kinetics study elucidated that the switchable Pt-(O-P) linkages with strong electronic-withdrawing function of PO43− (Pt1-OPO43− active site) not only realize the activation of C-H bond, but also destabilize the transition state from adsorbed hydroxy acids toward the C-C cleavage, resulting in the sharply increased selectivity of hydroxy acids. Moreover, the strong PO43−-coordination effect, originating from the enhanced interaction between positively charged Pt1 and negatively charged OPO43−, provides electrostatic stabilization for the atomically dispersed Pt, ensuring the highly efficient catalysis of Pt1/HAP for over 160 hours without metal leaching. This finding opens up new opportunities for efficient upgrading of bio-polyols over atomically dispersed catalysts.
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