Hydrogen Donor Molecules Research Articles

Exploring Hydrogen Sources in Catalytic Transfer Hydrogenation: A Review of Unsaturated Compound Reduction.

Catalytic transfer hydrogenation has emerged as a pivotal chemical process with transformative potential in various industries. This review highlights the significance of catalytic transfer hydrogenation, a reaction that facilitates the transfer of hydrogen from one molecule to another, using a distinct molecule as the hydrogen source in the presence of a catalyst. Unlike conventional direct hydrogenation, catalytic transfer hydrogenation offers numerous advantages, such as enhanced safety, cost-effective hydrogen donors, byproduct recyclability, catalyst accessibility, and the potential for catalytic asymmetric transfer hydrogenation, particularly with chiral ligands. Moreover, the diverse range of hydrogen donor molecules utilized in this reaction have been explored, shedding light on their unique properties and their impact on catalytic systems and the mechanism elucidation of some reactions. Alcohols such as methanol and isopropanol are prominent hydrogen donors, demonstrating remarkable efficacy in various reductions. Formic acid offers irreversible hydrogenation, preventing the occurrence of reverse reactions, and is extensively utilized in chiral compound synthesis. Unconventional donors such as 1,4-cyclohexadiene and glycerol have shown a good efficiency in reducing unsaturated compounds, with glycerol additionally serving as a green solvent in some transformations. The compatibility of these donors with various catalysts, substrates, and reaction conditions were all discussed. Furthermore, this paper outlines future trends which include the utilization of biomass-derived hydrogen donors, the exploration of hydrogen storage materials such as metal-organic frameworks (MOFs), catalyst development for enhanced activity and recyclability, and the utilization of eco-friendly solvents such as glycerol and ionic liquids. Innovative heating methods, diverse base materials, and continued research into catalyst-hydrogen donor interactions are aimed to shape the future of catalytic transfer hydrogenation, enhancing its selectivity and efficiency across various industries and applications.

Catalytic valorization of glycerol in the absence of external hydrogen: Effect of the Cu/ZrO2 catalyst mass and solvent

The glycerol valorization by heterogeneous catalysis to produce high-value-added chemicals is mainly carried out in the presence of high pressures of molecular hydrogen, a highly flammable gas whose main production in our days depends on fossil fuels. Therefore, an attractive alternative to explore is hydrogen in-situ generation in the catalytic process. Herein, we investigated the liquid-phase catalytic valorization of 80% wt. glycerol in different solvents such as water, 2-propanol, and acetone using a Cu/ZrO2 catalyst in the absence of external hydrogen. Firstly, the mass effect of the Cu/ZrO2 in the glycerol aqueous medium was evaluated finding an optimum mass of 250 mg for glycerol conversion. At these conditions, an initial reaction rate value of 2.63 × 10−3 molgly·gcat−1·min−1 was observed while the main products were hydroxyacetone (HA) and 1,2-propanediol (1,2-PDO). The use of 2-propanol as solvent and hydrogen donor molecule in the glycerol conversion induced the hydrogenation of hydroxyacetone towards 1,2-PDO. The ratio between the selectivity of 1,2-PDO/HA was found to be higher than that observed for the catalytic experiment with water. For the conversion of glycerol in the presence of acetone as a solvent it was noted the occurrence of acetalization reaction of glycerol with acetone and the main product observed was 4-hydroxymethyl-2,2-dimethyl-1,3-dioxalane or solketal. Density functional theory (DFT) calculations were included to gain insight into the reaction mechanisms of the hydroxyacetone hydrogenation to the formation of 1,2-PDO on Cu/ZrO2 catalyst. Four possible pathways were considered. The elementary steps include several intramolecular hydrogen atom transfer steps and two hydrogen addition steps. The hydrogen sources would come from adsorbed hydroxyl species of the aqueous reaction medium on ZrO2 support.

Energy Densification of Biomass-Derived Furfurals to Furanic Biofuels by Catalytic Hydrogenation and Hydrodeoxygenation Reactions

The concomitant hydrolysis and dehydration of biomass-derived cellulose and hemicellulose to furfural (FUR) and 5-(hydroxymethyl)furfural (HMF) under acid catalysis allows a dramatic reduction in the oxygen content of the parent sugar molecules with a 100% carbon economy. However, most applications of FUR or HMF necessitate synthetic modifications. Catalytic hydrogenation and hydrogenolysis have been recognized as efficient strategies for the selective deoxygenation and energy densification of biomass-derived furfurals generating water as the sole byproduct. Efficient and eco-friendly catalysts have been developed for the selective hydrogenation of furfurals affording renewable furanic compounds such as 2-methylfuran, 2,5-dimethylfuran and 2-methyltetrahydrofuran with potential applications as biofuel, solvent and chemical feedstock. Hydrogen gas or hydrogen donor molecules, required for the above processes, can also be renewably obtained from biomass using catalytic processes, enabling a circular economy. In this review, the recent developments in the energy densification of furfurals to furanic compounds of commercial significance are elaborated, emphasizing the role of catalyst and the reaction parameters employed. Critical discussion on sourcing hydrogen gas required for the processes, using hydrogen donor solvents, catalyst design and the potential markets of furanic intermediates have been made. Critical evaluations of the accomplishments and challenges in this field are also provided.

Recent advances in heterogeneous catalytic transfer hydrogenation/hydrogenolysis for valorization of biomass-derived furanic compounds

Catalytic transfer hydrogenation/hydrogenolysis can valorize renewable compounds derived from biomass. Different catalysts have the ability to transfer hydrogen from hydrogen-donor molecules thereby avoiding the use of hazardous gaseous hydrogen.

Heterogeneous Catalyzed Thermochemical Conversion of Lignin Model Compounds: An Overview.

Thermochemical lignin conversion processes can be described as complex reaction networks involving not only de-polymerization and re-polymerization reactions, but also chemical transformations of the depolymerized mono-, di-, and oligomeric compounds. They typically result in a product mixture consisting of a gaseous, liquid (i.e., mono-, di-, and oligomeric products), and solid phase. Consequently, researchers have developed a common strategy to simplify this issue by replacing lignin with simpler, but still representative, lignin model compounds. This strategy is typically applied to the elucidation of reaction mechanisms and the exploration of novel lignin conversion approaches. In this review, we present a general overview of the latest advances in the principal thermochemical processes applied for the conversion of lignin model compounds using heterogeneous catalysts. This review focuses on the most representative lignin conversion methods, i.e., reductive, oxidative, pyrolytic, and hydrolytic processes. An additional subchapter on the reforming of pyrolysis oil model compounds has also been included. Special attention will be given to those research papers using "green" reactants (i.e., H2 or renewable hydrogen donor molecules in reductive processes or air/O2 in oxidative processes) and solvents, although less environmentally friendly chemicals will be also considered. Moreover, the scope of the review is limited to those most representative lignin model compounds and to those reaction products that are typically targeted in lignin valorization.

Preparation of single chain nanoparticles via photoinduced radical coupling process

This contribution introduces a straightforward method for preparing well-defined polymeric nanoparticles using radical coupling process of ketyl moieties resulted from triplet excitation of pendant benzophenone groups. In the first step, poly(styrene-co-chloromethylstyrene) is synthesized by thermally initiated controlled radical copolymerization technique and subsequently, pendant chloride groups undergo post-modification with 4–hydroxybenzophenone. Achieved well-defined side–chain benzophenone containing copolymers generate ketyl radicals in the presence of excess hydrogen donor molecule upon UV-light irradiation and intramolecularly crosslinked nanoparticles are formed by radical coupling process in dilute regime. Resulting single chain nanoparticles and intermediates are characterized by 1H NMR, gel permeation chromatography, differential scanning calorimetry, UV–Vis spectrometry and electron microscopy techniques.

Alumina-Supported Gold Nanoparticles as a Bifunctional Catalyst for the Synthesis of 2-Amino-3-arylimidazo[1,2-a]pyridines.

The bifunctional catalytic efficacy of alumina-supported gold nanoparticles (Au/Al2O3) was investigated for the synthesis of a series of 2-amino-3-aryl-imidazopyridines through the chemoselective reduction of the corresponding 2-nitro-3-aryl-imidazo[1,2-a]pyridines in high isolated yields. This highly efficient protocol was initially applied for the synthesis of 2-nitro-3-aryl imidazo[1,2-a]pyridines via the reaction between 2-aminopyridine and nitroalkenes catalyzed by the present catalytic system Au/Al2O3. Moreover, the heterogeneous surface γ-Al2O3 was also found to catalyze this pathway in a comparable manner. However, only Au/Al2O3 was further proved as the appropriate catalytic system for the selective transfer hydrogenation of the synthesized 2-nitro imidazopyridine derivatives into the corresponding 2-amino-3-aryl imidazo[1,2-a]pyridines using NaBH4 as a hydrogen-donor molecule. In addition, the one-pot two-step reaction between nitroalkenes and aminopyridines in the presence of Au/Al2O3–NaBH4 provided directly the fast and facile synthesis of 2-amino-3-aryl imidazopyridines, highlighting a useful synthetic application of the catalytic protocol.

Unraveling the Role of Formic Acid and the Type of Solvent in the Catalytic Conversion of Lignin: A Holistic Approach

The role of formic acid together with the effect of the solvent type and their synergic interactions with a NiMo catalyst were studied for the conversion of lignin into bio-oil in an alcohol/formic acid media. The replacement of formic acid with H2 or isopropanol decreased the oil yield to a considerable degree, increased the solid yield, and altered the nature of the bio-oil. The differences induced by the presence of H2 were comparable to those observed in the isopropanol system, which suggests similar lignin conversion mechanisms for both systems. Additional semi-batch experiments confirmed that formic acid does not act merely as an in situ hydrogen source or hydrogen donor molecule. Actually, is seems to react with lignin through a formylation-elimination-hydrogenolysis mechanism that leads to the depolymerization of the biopolymer. This reaction competes with formic acid decomposition, which gives mainly H2 and CO2 , and forms a complex reaction system. To the best of our knowledge, this is the first time that the distinctive role/mechanism of formic acid has been observed in the conversion of real lignin feedstock. In addition, the solvent, especially ethanol, seems also to play a vital role in the stabilization of the depolymerized monomers and in the elimination/deformylation step.

Photoinduced hydrogen-bonding dynamics.

Hydrogen bonding dynamics has received extensive research attention in recent years due to the significant advances in femtolaser spectroscopy experiments and quantum chemistry calculations. Usually, photoexcitation would cause changes in the hydrogen bonding formed through the interaction between hydrogen donor and acceptor molecules on their ground electronic states, and such transient strengthening or weakening of hydrogen bonding could be crucial for the photophysical transformations and the subsequent photochemical reactions that occurred on a time scale from tens of femtosecond to a few nanoseconds. In this article, we review the combined experimental and theoretical studies focusing on the ultrafast electronic and vibrational hydrogen bonding dynamics. Through these studies, new mechanisms and proposals and common rules have been put forward to advance our understanding of the hydrogen bondings dynamics in a variety of important photoinduced phenomena like photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer processes, chemosensor fluorescence sensing, rearrangements of the hydrogen-bond network including forming and breaking hydrogen bond in water. Graphical Abstract We review the recent advances on exploring the photoinduced hydrogen bonding dynamics in solutions through a joint approach of laser spectroscopy and theoretical calculation. The reviewed studies have put forward a new mechanism, new proposal, and new rule for a variety of photoinduced phenomena such as photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer, chemosensor fluorescence sensing, and rearrangements of the hydrogen-bond network in water.

Sodium Conversion of Oilsands Bitumen-Derived Asphaltenes

Alkali metals are strong electron donors and can form electron donor–acceptor ion pairs with multinuclear aromatics. Single electron donation converts the aromatic into a radial ion, and two electron donations convert the aromatic into a dianion. The anionic aromatic species are more susceptible to reductive addition reactions, such as hydrogen transfer from more hydrogen-rich molecules, such as employed in Birch reduction. The conversion of heavy oils in the presence of alkali metals is claimed to be capable of bulk desulfurization with little hydrogen consumption. In this work, the conversion of oilsands bitumen asphaltenes with sodium was investigated over the temperature range of 60–250 °C under an inert atmosphere to limit the contribution of thermal conversion. Control experiments conducted with asphaltenes without sodium revealed that the asphaltenes were reactive on their own, and the nature of products was affected by the phase behavior of the asphaltenes that gradually changed from a solid to liquid between 124 and 142 °C. When fluidity was limited, intermolecular hydrogen transfer was restricted; intramolecular hydrogen disproportionation and “in cage” intermolecular reactions resulted in the formation of more condensed and potentially more aromatic products. Sodium markedly affected the natural hydrogen transfer and disproportionation. Conversion of the asphaltenes with sodium did not result in an increased maltene yield, but the maltenes had a higher hydrogen/carbon ratio, less sulfur, and less nitrogen. Model compound reactions were employed to study the influence of the reaction atmosphere (N2 or H2) and hydrogen donor properties of the organic matrix. In the presence of H2, the formation and reaction of NaH appeared to influence selectivity and the reaction network. In the absence of H2, desulfurization of thiophenic compounds by sodium proceeded by hydrogenolysis and hydrogenation pathways, with the hydrogenolysis pathway being favored by the lack of hydrogen donor molecules. It was also found that hydrogenolysis of the carbon–carbon bond in the thiophenic ring of dibenzothiophene is reversible.

Economic assessment for the production of 1,2‐Propanediol from bioglycerol hydrogenolysis using molecular hydrogen or hydrogen donor molecules

The 1,2‐propanediol can be obtained from bio‐glycerol through hydrogenolysis reactions. The hydrogen required in the process can be supplied using high molecular hydrogen pressure or hydrogen donor molecules, formic acid being the most attractive donor. An economical assessment of both alternatives for hydrogen supply was carried out. Results from the conceptual design of the 1,2‐propanediol purification process revealed that the separation of water from glycols is the most expensive step. The use of formic acid can be cost effective only if it is available at a price lower than 0.12 € kg−1 and high initial glycerol aqueous solutions are used. The formation of condensation products from highly concentrated glycerol solutions when using hydrogen donors needs to be avoided. © 2015 American Institute of Chemical Engineers Environ Prog, 35:447–454, 2016

Intermolecular hydrogen-bonding effects on photophysics and photochemistry

Intermolecular hydrogen bonding, as an important site-specific interaction between hydrogen donor and acceptor molecules both in the gas phase and in solution, plays a significant role and has a remarkable influence on the photophysics and photochemistry of chromophores in the hydrogen-bonding surroundings. In recent years, the excited-state structures and dynamics of the intermolecular hydrogen bonding have been widely investigated by using both the experimental and theoretical methods. This review article focuses on the recent research progress of the important intermolecular hydrogen-bonding effects on the non-adiabatic photophysical processes and photochemical reactions. Firstly, the corresponding relationship between electronic spectral red-shift or blue-shift and excited-state intermolecular hydrogen bond strengthening or weakening has been clarified. A dynamic equilibrium induced by the intermolecular hydrogen bond strengthening in the electronically excited state of fluorenone chromophore was used to explain the steady-state spectral features. The stepwise mechanism of excited-state double proton transfer reaction for the 2-aminopyridine/acid systems was demonstrated. The role of intermolecular hydrogen bonding on the excited-state proton transfer in the sensing mechanism of fluorescent probes has also been discussed. Moreover, a dihydrogen-bonded complex formed by borane-trimethylamine and phenol showed interesting geometric structures and infared spectrum in electronically excited state.

Cooperative Roles of Charge Transfer and Dispersion Terms in Hydrogen-Bonded Networks of (H2O)n, n = 6, 11, and 16

The perturbation expansion based on the locally-projected molecular orbital (LPMO PT) was applied to the study of the hydrogen-bonded networks of water clusters with up to 16 molecules. Utilizing the local nature of the occupied and excited MOs on each monomer, the charge-transfer and dispersion terms are evaluated for every pair of molecules. The two terms are strongly correlated with each other for the hydrogen-bonded pairs. The strength of the hydrogen bonds in the clusters is further classified by the types of the hydrogen donor and acceptor water molecules. The relative energies evaluated with the LPMO PT among the isomers of (H2O)6, (H2O)11, and (H2O)16 agree very well with those obtained from CCSD(T) calculations with large basis sets. The binding energy of the LPMO PT is approximately free of the basis set superposition errors caused both by the orbital basis inconsistency and by the configuration basis inconsistency.

Reinvestigation of homoaromaticity of cyclohepta-1,3,5-triene

A reinvestigation of the homoaromaticity of cyclohepta-1,3,5-triene has been done at the DFT (B3LYP/6-31+G*) level. The determination of the aromatic stabilization energies based on the hypohomodesmotic reactions gives either too high value (−19.58kcalmol−1 using ethane as the hydrogen donor molecule) or too low values (−0.46kcalmol−1 using cycloheptane or −4.27kcalmol−1 using cyclopentane molecules as the hydrogen donor molecules), as the ring strains on the two sides of the reactions are not compensated. The isomerisation reaction of methylenecyclohepta-1,3-diene to 1-methylcyclohepta-1,3,5-triene gives a value of −10.68kcalmol−1 as the isomerisation energy. Investigation of the valence tautomerization of cyclohepta-1,3,5-triene to norcaradiene and back to cyclohepta-1,3,5-triene reveals that a dynamic equilibrium exists between the two valence tautomers due to small activation energy barriers, which causes strong interactions between the π orbitals of the triene moiety and the HCCH2CHσ orbitals. The NBO analysis of the two valence tautomers and the transition structure involved therein support these interactions. The Frontier Molecular Orbitals of cyclohepta-1,3,5-triene, norcaradiene and the transition structure depict unambiguously the formation of the annular electron cloud, which confers homoaromatic character on cyclohepta-1,3,5-triene.

Impact of proton diffusion and the hydrogen photospillover upon the photochromic sensitivity of the WO3 films and the WO3 double-layer structures

It has been shown that the hydrogen photochromism, i.e., photochromism arising in WO3 films due to hydrogen atoms detached from hydrogen donor molecules under the action of light, is massively impacted by proton diffusion. The control of the diffusion can be established by the combined use of two types of hydrogen-containing molecules; one (organic) playing the role of the hydrogen donor, whereas the other (water) provides pathways for the proton diffusion. The film morphology highly influences formation of the proton conducting water wires in pores of the WO3 films. The spirit is that the hydrogen photospillover is used here: the hydrogen atoms detached from the hydrogen donor molecules adsorbed on the surface of the highly disordered WO3 films flow to the polycrystalline WO3 films along the special water pathways that are formed in the highly disordered films. The hydrogen spillover triggered by light makes it possible to create the photochromic systems with enhanced photochromic sensitivity and special optical characteristics of the photochromic state.

Glycerol hydrogenolysis into propanediols using in situ generated hydrogen – A critical review

AbstractThe rise in chemical transesterification of plant triglycerides towards biodiesel is unbowed and thus the available amount of glycerol is still increasing. The produced amount overruns the chemically used portion. Various ways to convert glycerol have been shown recently to yield attractive intermediates and final products. One of the options of future chemical utilisation of glycerol might be its conversion to propanediols (1,2‐PDO (propylene glycol), 1,3‐PDO (trimethylene glycol)) by hydrogenolysis. 1,2‐PDO finds various applications in chemical industries; 1,3‐PDO is mainly used for the manufacture of polymers. A synthesis route via glycerol might substitute present industrial syntheses using for example propylene oxide. Such an alternative synthesis route might run in the presence of externally fed hydrogen or by use of in situ generated hydrogen that can be supplied for example by glycerol aqueous phase reforming (APR) and/or catalytic transfer hydrogenation (CTH) using hydrogen donor molecules. A very attractive approach seems to be the use of formic acid as hydrogen donor for CTH because only carbon dioxide is liberated as a by‐product. This paper summarises most significant reports of the last decade, dealing with the production of PDOs via glycerol hydrogenolysis by in situ generated hydrogen.

Hydrogenolysis through catalytic transfer hydrogenation: Glycerol conversion to 1,2-propanediol

Important biorefinery processes imply hydrogenolysis reactions where high hydrogen pressures are required. As most of the nowadays available hydrogen gas is produced from fossil fuels there are great incentives to develop alternative technologies able to both substitute non-renewable reactants and operate at lower severity conditions. The use of hydrogen donor molecules from renewable origin can be a promising alternative to tackle simultaneously with both objectives. In the present study the use of methanol, 2-propanol and formic acid in the glycerol hydrogenolysis process to obtain 1,2-propanediol was investigated using a Ni–Cu/Al2O3 catalyst, prepared by sol–gel method, and under N2 atmosphere. A semi-continuous set-up was designed in which the donor solution was continuously fed into the autoclave reactor containing the glycerol aqueous phase. The best results in terms of glycerol conversion and 1,2-propanediol selectivity were obtained with formic acid.

Liquid-phase glycerol hydrogenolysis by formic acid over Ni–Cu/Al2O3 catalysts

Two series of Ni–Cu/Al2O3 catalysts with different Cu/Ni ratio and different total metal contents were prepared and tested in the glycerol hydrogenolysis to 1,2-propanediol under N2 pressure and using formic acid as hydrogen donor molecule. The results from the deep characterization of the catalysts by N2-physisorption, transmission electron microscopy (TEM), temperature-programed reduction (TPR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and temperature-programed desorption of ammonia (TPD-NH3), together with the results from the activity tests allowed deeper understanding of the role played by Ni, Cu, and acid catalytic sites. The kinetic study performed with the optimized catalyst revealed that the OH groups of glycerol and of the target product, 1,2-propanediol, compete for adsorption on the acid sites of the Al2O3 support. 90% glycerol conversion and 82% 1,2-propanediol selectivity after 24h reaction time were achieved when operating at 493K.

Hydrogen Bonding in the Electronic Excited State

Because of its fundamental importance in many branches of science, hydrogen bonding is a subject of intense contemporary research interest. The physical and chemical properties of hydrogen bonds in the ground state have been widely studied both experimentally and theoretically by chemists, physicists, and biologists. However, hydrogen bonding in the electronic excited state, which plays an important role in many photophysical processes and photochemical reactions, has scarcely been investigated. Upon electronic excitation of hydrogen-bonded systems by light, the hydrogen donor and acceptor molecules must reorganize in the electronic excited state because of the significant charge distribution difference between the different electronic states. The electronic excited-state hydrogen-bonding dynamics, which are predominantly determined by the vibrational motions of the hydrogen donor and acceptor groups, generally occur on ultrafast time scales of hundreds of femtoseconds. As a result, state-of-the-art femtosecond time-resolved vibrational spectroscopy is used to directly monitor the ultrafast dynamical behavior of hydrogen bonds in the electronic excited state. It is important to note that the excited-state hydrogen-bonding dynamics are coupled to the electronic excitation. Fortunately, the combination of femtosecond time-resolved spectroscopy and accurate quantum chemistry calculations of excited states resolves this issue in laser experiments. Through a comparison of the hydrogen-bonded complex to the separated hydrogen donor or acceptor in ground and electronic excited states, the excited-state hydrogen-bonding structure and dynamics have been obtained. Moreover, we have also demonstrated the importance of hydrogen bonding in many photophysical processes and photochemical reactions. In this Account, we review our recent advances in electronic excited-state hydrogen-bonding dynamics and the significant role of electronic excited-state hydrogen bonding on internal conversion (IC), electronic spectral shifts (ESS), photoinduced electron transfer (PET), fluorescence quenching (FQ), intramolecular charge transfer (ICT), and metal-to-ligand charge transfer (MLCT). The combination of various spectroscopic experiments with theoretical calculations has led to tremendous progress in excited-state hydrogen-bonding research. We first demonstrated that the intermolecular hydrogen bond in the electronic excited state is greatly strengthened for coumarin chromophores and weakened for thiocarbonyl chromophores. We have also clarified that the intermolecular hydrogen-bond strengthening and weakening correspond to red-shifts and blue-shifts, respectively, in the electronic spectra. Moreover, radiationless deactivations (via IC, PET, ICT, MLCT, and so on) can be dramatically influenced through the regulation of electronic states by hydrogen-bonding interactions. Consequently, the fluorescence of chromophores in hydrogen-bonded surroundings is quenched or enhanced by hydrogen bonds. Our research expands our understanding of the nature of hydrogen bonding by delineating the interaction between hydrogen bonds and photons, thereby providing a basis for excited-state hydrogen bonding studies in photophysics, photochemistry, and photobiology.

Liquid-phase glycerol hydrogenolysis to 1,2-propanediol under nitrogen pressure using 2-propanol as hydrogen source

2-Propanol was studied as a hydrogen donor molecule in the transfer hydrogenation process to selectively convert glycerol into 1,2-propanediol under N 2 pressure and using Ni or/and Cu supported on Al 2O 3 catalysts. The results were compared to those obtained under the same operating conditions but under H 2 pressure. The results of the activity tests and catalyst characterization techniques (N 2-physisorption, H 2-chemisorption, TPD of NH 3, TPR, TPO and XPS) suggest that glycerol hydrogenolysis to yield 1,2-propanediol occurred through a different mechanism regarding the origin of the hydrogen species. When atomic hydrogen came from dissolved molecular hydrogen dissociation, glycerol was first dehydrated to acetol and then hydrogenated to 1,2-propanediol. On the other hand, when the hydrogen atoms were produced from 2-propanol dehydrogenation, glycerol was directly converted to 1,2-propanediol through intermediate alkoxide formation.