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The conversion of biomass-derived glycerol into valuable products is an alternative strategy for alleviating energy scarcity and environmental issues. The authors recently uncovered an activated carbon composite electrode with an Amberlyst-15 mediator able to generate 1,2-propanediol, diethylene glycol, and acetol via a glycerol electrocatalytic reduction. However, less attention to mechanistic insights makes its application to industrial processes challenging. Herein, two proposed intermediates, acetol and ethylene glycol, were employed as the feedstocks to fill the gap in the mechanistic understanding of the reactions. The results discovered the importance of acetol in producing 1,2-propanediol and concluded the glycerol electrocatalytic reduction process has a two-step reduction pathway, where glycerol was initially reduced to acetol and consecutively hydrogenated to 1,2-propanediol. At 353 K and 0.28 A/cm2, 1,2-propanediol selectivity achieved 77% (with 59.8 C mol% yield) after 7 h of acetol (3.0 mol/L) electrolysis. Finally, the influences of the temperature, glycerol initial concentration, and current density on the glycerol electrocatalytic reduction were evaluated. The initial step involved the C-O and C-C bonds cleavage in glycerol plays a crucial role in producing either acetol or ethylene glycol intermediate. This was controlled by the temperature, which low to moderate value is needed to maintain a selective acetol-1,2-propanediol route. Additionally, medium glycerol initial concentration reduced the hydrogen formation and indirectly improved 1,2-propanediol yield. A mild current density raised the conversion rate and minimized the growth of intermediates. At 353 K and 0.21 A/cm2, glycerol (3.0 mol/L) electrocatalytic reduction to 1,2-propanediol reached the maximum yield of 42.3 C mol%.

The conversion of biomass-derived glycerol into valuable products is an alternative strategy for alleviating energy scarcity and environmental issues. The authors recently uncovered an activated carbon composite electrode with an Amberlyst-15 mediator able to generate 1,2-propanediol, diethylene glycol, and acetol via a glycerol electrocatalytic reduction. However, less attention to mechanistic insights makes its application to industrial processes challenging. Herein, two proposed intermediates, acetol and ethylene glycol, were employed as the feedstocks to fill the gap in the mechanistic understanding of the reactions. The results discovered the importance of acetol in producing 1,2-propanediol and concluded the glycerol electrocatalytic reduction process has a two-step reduction pathway, where glycerol was initially reduced to acetol and consecutively hydrogenated to 1,2-propanediol. At 353 K and 0.28 A/cm2, 1,2-propanediol selectivity achieved 77% (with 59.8 C mol% yield) after 7 h of acetol (3.0 mol/L) electrolysis. Finally, the influences of the temperature, glycerol initial concentration, and current density on the glycerol electrocatalytic reduction were evaluated. The initial step involved the C-O and C-C bonds cleavage in glycerol plays a crucial role in producing either acetol or ethylene glycol intermediate. This was controlled by the temperature, which low to moderate value is needed to maintain a selective acetol-1,2-propanediol route. Additionally, medium glycerol initial concentration reduced the hydrogen formation and indirectly improved 1,2-propanediol yield. A mild current density raised the conversion rate and minimized the growth of intermediates. At 353 K and 0.21 A/cm2, glycerol (3.0 mol/L) electrocatalytic reduction to 1,2-propanediol reached the maximum yield of 42.3 C mol%.

Glycerol electrooxidation has attracted immense attention due to the economic advantage it could add to biodiesel production. One of the significant challenges for the industrial development of glycerol electrooxidation process is the search for a suitable electrocatalyst that is sustainable, cost effective, and tolerant to carbonaceous species, results in high performance, and is capable of replacing the conventional Pt/C catalyst. We review suitable, sustainable, and inexpensive alternative electrocatalysts with enhanced activity, selectivity, and durability, ensuring the economic viability of the glycerol electrooxidation process. The alternatives discussed here include Pd-based, Au-based, Ni-based, and Ag-based catalysts, as well as the combination of two or three of these metals. Also discussed here are the prospective materials that are yet to be explored for glycerol oxidation but are reported to be bifunctional (being capable of both anodic and cathodic reaction). These include heteroatom-doped metal-free electrocatalysts, which are carbon materials doped with one or two heteroatoms (N, B, S, P, F, I, Br, Cl), and heteroatom-doped nonprecious transition metals. Rational design of these materials can produce electrocatalysts with activity comparable to that of Pt/C catalysts. The takeaway from this review is that it provides an insight into further study and engineering applications on the efficient and cost-effective conversion of glycerol to value-added chemicals.

This study explores the mechanistic, kinetic process and parameters of nitrogen and fluorine-doped activated carbon black composite catalyst during glycerol electrooxidation in alkaline so under some precise experimental parameters. The influence of catalyst and electrochemical impedance spectroscopy (EIS) perturbation amplitude were systematically studied. The kinetic parameters from steady-state measurement and microkinetic modelling study reveal that glycerol electrooxidation undergoes complicated mechanism. From the chronoamperometry study, the nitrogen-doped sample (ACB-N2) shows a remarkable activity and stability, but the performance was improved upon the simultaneous doping of fluorine to form ACB-N2F2. The best rate constant was obtained by ACB-N2F2 (7.335 × 10−3), which is by far greater than those of ACB-N2 (2.533 × 10−3) and ACB-F2 (2.012 × 10−3) for steady-state. The slope obtained from the Tafel plot of both the voltammetry and the non-linear electrochemical impedance spectroscopy measurement also confirms the superior performance of ACB-N2F2 compared to ACB-N2 and ACB-F2. The rate constant of ACB-N2F2 is almost 6 times of that of ACB-N2, and 4 times of the of ACB-F2 for the forward sweep. The exchange current density of ACB-N2F2 is almost 7 times of that of ACB-N2, and 3 times of the of ACB-F2 for the forward sweep. The methods in this study for evaluation of glycerol electrooxidation kinetic process and kinetic parameters could be used to investigate other electrocatalysts.

This study explores the mechanistic, kinetic process and parameters of nitrogen and fluorine-doped activated carbon black composite catalyst during glycerol electrooxidation in alkaline so under some precise experimental parameters. The influence of catalyst and electrochemical impedance spectroscopy (EIS) perturbation amplitude were systematically studied. The kinetic parameters from steady-state measurement and microkinetic modelling study reveal that glycerol electrooxidation undergoes complicated mechanism. From the chronoamperometry study, the nitrogen-doped sample (ACB-N2) shows a remarkable activity and stability, but the performance was improved upon the simultaneous doping of fluorine to form ACB-N2F2. The best rate constant was obtained by ACB-N2F2 (7.335 × 10−3), which is by far greater than those of ACB-N2 (2.533 × 10−3) and ACB-F2 (2.012 × 10−3) for steady-state. The slope obtained from the Tafel plot of both the voltammetry and the non-linear electrochemical impedance spectroscopy measurement also confirms the superior performance of ACB-N2F2 compared to ACB-N2 and ACB-F2. The rate constant of ACB-N2F2 is almost 6 times of that of ACB-N2, and 4 times of the of ACB-F2 for the forward sweep. The exchange current density of ACB-N2F2 is almost 7 times of that of ACB-N2, and 3 times of the of ACB-F2 for the forward sweep. The methods in this study for evaluation of glycerol electrooxidation kinetic process and kinetic parameters could be used to investigate other electrocatalysts.

The present investigation aimed to study the physicochemical characteristics of supported catalysts comprising various percentages of zinc dispersed over SiO2. The physiochemical properties of these catalysts were surveyed by N2physisorption (BET), thermogravimetry analysis (TGA), H2temperature-programmed reduction, field-emission scanning electron microscopy (FESEM), inductively coupled plasma-optical emission spectrometry (ICP-OES), and NH3temperature-programmed desorption (NH3-TPD). In addition, to examine the activity and performance of the catalysts for the hydrodeoxygenation (HDO) of the bio-oil oxygenated compounds, the experimental reaction runs, as well as stability and durability tests, were performed using 3% Zn/SiO2as the catalyst. Characterization of silica-supported zinc catalysts revealed an even dispersion of the active site over the support in the various dopings of the zinc. The acidity of the calcinated catalysts elevated clearly up to 0.481 mmol/g. Moreover, characteristic outcomes indicate that elevating the doping of zinc metal led to interaction and substitution of proton sites on the SiO2surface that finally resulted in an increase in the desorption temperature peak. The experiments were performed at temperature 500 °C, pressure 1 atm; weight hourly space velocity (WHSV) 0.32 (h-1); feed flow rate 0.5 (mL/min); and hydrogen flow rate 150 (mL/min). Based on the results, it was revealed that among all the prepared catalysts, that with 3% of zinc had the highest conversion efficiency up to 80%. However, the selectivity of the major products, analyzed by gas chromatography flame-ionization detection (GC-FID), was not influenced by the variation in the active site doping.

Glycerol is a by-product produced from biodiesel, fatty acid, soap and bioethanol industries. Today, the value of glycerol is decreasing in the global market due to glycerol surplus, which primarily resulted from the speedy expansion of biodiesel producers around the world. Numerous studies have proposed ways of managing and treating glycerol, as well as converting it into value-added compounds. The electrochemical conversion method is preferred for this transformation due to its simplicity and hence, it is discussed in detail. Additionally, the factors that could affect the process mechanisms and products distribution in the electrochemical process, including electrodes materials, pH of electrolyte, applied potential, current density, temperature and additives are also thoroughly explained. Value-added compounds that can be produced from the electrochemical conversion of glycerol include glyceraldehyde, dihydroxyacetone, glycolic acid, glyceric acid, lactic acid, 1,2-propanediol, 1,3-propanediol, tartronic acid and mesoxalic acid. These compounds are found to have broad applications in cosmetics, pharmaceutical, food and polymer industries are also described. This review will be devoted to a comprehensive overview of the current scenario in the glycerol electrochemical conversion, the factors affecting the mechanism pathways, reaction rates, product selectivity and yield. Possible outcomes obtained from the process and their benefits to the industries are discussed. The utilization of solid acid catalysts as additives for future studies is also suggested.

The hydrodeoxygenation (HDO) of phenol catalyzed by Zn/SiO2 under atmospheric H2 pressure was investigated in a continuous fixed bed reactor. The effects of several process parameters (zinc load, reaction temperature, weight hourly space velocity (WHSV), and H2 volumetric flow rate) were evaluated to optimize process conditions. Phenol was selected as a stable model component for lignin degradation products in fast pyrolysis bio-oil. Silica-supported zinc catalysts were prepared with different loadings of the active metal (0.5%, 1%, 2%, 3%, and 4%) and assessed using characterization techniques such as XRD, ICP-OES, BET, H2-TPR/TPD, and FESEM–EDX. Reaction products including benzene, cyclohexene, and cyclohexane were identified through GC/FID analysis. Experimental results revealed that process yield increased with reaction temperature, metal loading, and WHSV. The selectivity percentages of the products were slightly changed by varying process parameters. Moreover, H2 volumetric flow rate exerted a negligible effect on product yield and selectivity.

The hydrodeoxygenation (HDO) of phenol catalyzed by Zn/SiO2 under atmospheric H2 pressure was investigated in a continuous fixed bed reactor. The effects of several process parameters (zinc load, reaction temperature, weight hourly space velocity (WHSV), and H2 volumetric flow rate) were evaluated to optimize process conditions. Phenol was selected as a stable model component for lignin degradation products in fast pyrolysis bio-oil. Silica-supported zinc catalysts were prepared with different loadings of the active metal (0.5%, 1%, 2%, 3%, and 4%) and assessed using characterization techniques such as XRD, ICP-OES, BET, H2-TPR/TPD, and FESEM–EDX. Reaction products including benzene, cyclohexene, and cyclohexane were identified through GC/FID analysis. Experimental results revealed that process yield increased with reaction temperature, metal loading, and WHSV. The selectivity percentages of the products were slightly changed by varying process parameters. Moreover, H2 volumetric flow rate exerted a negligible effect on product yield and selectivity.

© 2020 MDPI AG. All rights reserved. The present investigation aimed to study the physicochemical characteristics of supported catalysts comprising various percentages of zinc dispersed over SiO2. The physiochemical properties of these catalysts were surveyed by N2physisorption (BET), thermogravimetry analysis (TGA), H2temperature-programmed reduction, field-emission scanning electron microscopy (FESEM), inductively coupled plasma-optical emission spectrometry (ICP-OES), and NH3temperature-programmed desorption (NH3-TPD). In addition, to examine the activity and performance of the catalysts for the hydrodeoxygenation (HDO) of the bio-oil oxygenated compounds, the experimental reaction runs, as well as stability and durability tests, were performed using 3% Zn/SiO2as the catalyst. Characterization of silica-supported zinc catalysts revealed an even dispersion of the active site over the support in the various dopings of the zinc. The acidity of the calcinated catalysts elevated clearly up to 0.481 mmol/g. Moreover, characteristic outcomes indicate that elevating the doping of zinc metal led to interaction and substitution of proton sites on the SiO2surface that finally resulted in an increase in the desorption temperature peak. The experiments were performed at temperature 500 °C, pressure 1 atm; weight hourly space velocity (WHSV) 0.32 (h-1); feed flow rate 0.5 (mL/min); and hydrogen flow rate 150 (mL/min). Based on the results, it was revealed that among all the prepared catalysts, that with 3% of zinc had the highest conversion efficiency up to 80%. However, the selectivity of the major products, analyzed by gas chromatography flame-ionization detection (GC-FID), was not influenced by the variation in the active site doping.

Hydrodeoxygenation (HDO) kinetics of phenol over Ag/TiO 2 catalyst was investigated at 415–600 K and 1 atm. The use of oxophilic TiO 2 support has improved phenol conversion due to its preferential activation of CO bond. Product analysis confirmed the occurrence of direct deoxygenation (DDO) and hydrogenation–dehydration (HYD) pathways to produce benzene and cyclohexane, respectively. Both phenol hydrogenolysis and hydrogenation steps are the respective rate-limiting steps for DDO and HYD pathways of phenol HDO over Ag/TiO 2 . Based on the transition state theory, negative entropy changes of activation during HDO indicated that the HDO reactants formed activated complexes that had more orderly bonding configurations prior to the hydrogenolysis, hydrogenation, and dehydration steps. Under the present conditions, the catalyst was stable after 4 hr of HDO runs and able to be regenerated via H 2 -activation and calcination in air at 553 K with at least 98.9% removal efficiency to remove coke deposits and reform Ag metal species after HDO.

Oil from the pyrolysis of biomass typically consists of two different layers defined as the aqueous and organic phases. The objective of this study was to determine the yield of liquid fuel that can be produced from the aqueous phase using a catalytic conversion. The process was supported by two different HZSM-5 catalysts with temperatures set at 405, 455, 505, and 555 °C. The oils obtained were then analyzed using Karl Fischer titration, FTIR spectroscopy, GC/MS, TGA, and CHNS/O analysis. The results showed that the oil yields obtained from catalytic cracking of the aqueous phase ranged from 4 to 9.16 wt % depending on the catalyst type and temperature. The optimum performance of deoxygenation activity was obtained with the HZSM-5/50 catalyst at a temperature of 555 °C. The oil produced under the optimum conditions was dominated by aromatics and phenols and had an HHV of 38.44 MJ/kg. © 2014 American Chemical Society.