The electrocatalytic hydrogenation of benzophenone was performed at room temperature and atmospheric pressure using a polymer electrolyte membrane electrochemical reactor (PEMER). Palladium (Pd) nanoparticles were synthesised and supported on a carbonaceous matrix (Pd/C) with a 28 wt % of Pd with respect to carbon material. Pd/C was characterised by transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). Cathodes were prepared using Pd electrocatalytic loadings (LPd) of 0.2 and 0.02 mg cm-2. The anode consisted of hydrogen gas diffusion for the electrooxidation of hydrogen gas, and a 117 Nafion exchange membrane acted as a cationic polymer electrolyte membrane. Benzophenone solution was electrochemically hydrogenated in EtOH/water (90/10 v/v) plus 0.1 M H2SO4. Current densities of 10, 15 and 20 mA cm-2 were analysed for the preparative electrochemical hydrogenation of benzophenone and such results led to the highest fractional conversion (XR) of around 30% and a selectivity over 90% for the synthesis of diphenylmethanol upon the lowest current density. With regards to an increase by ten times the Pd electrocatalytic loading the electrocatalytic hydrogenation led neither to an increase in fractional conversion nor to a change in selectivity.

First-row transition-metal complexes hold great potential as catalysts for hydrogenations and related reductive reactions. Homo- and heteroleptic arene/alkene metalates(1-) (M=Co, Fe) are a structurally distinct catalyst class with good activities in hydrogenations of alkenes and alkynes. The first syntheses of the heteroleptic cobaltates [K([18]crown-6)][Co(η4 -cod)(η2 -styrene)2 ] (5) and [K([18]crown-6)][Co(η4 -dct)(η4 -cod)] (6), and the homoleptic complex [K(thf)2 ][Co(η4 -dct)2 ] (7; dct=dibenzo[a,e]cyclooctatetraene, cod=1,5-cyclooctadiene), are reported. For comparison, two cyclopentadienylferrates(1-) were synthesized according to literature procedures. The isolated and fully characterized monoanionic complexes were competent precatalysts in alkene hydrogenations under mild conditions (2 bar H2 , r.t., THF). Mechanistic studies by NMR spectroscopy, ESI mass spectrometry, and poisoning experiments documented the operation of a homogeneous mechanism, which was initiated by facile redox-neutral π-ligand exchange with the substrates followed by H2 activation. The substrate scope of the investigated precatalysts was also extended to polar substrates (ketones and imines).

Despite the large number of studies on the catalytic hydrogenation of CO2 to CO and hydrocarbons by metal nanoparticles, the nature of the active sites and the reaction mechanism have remained unresolved. This hampers the development of effective catalysts relevant to energy storage. By investigating the structure sensitivity of CO2 hydrogenation on a set of silica-supported Ni nanoparticle catalysts (2-12 nm), we found that the active sites responsible for the conversion of CO2 to CO are different from those for the subsequent hydrogenation of CO to CH4. While the former reaction step is weakly dependent on the nanoparticle size, the latter is strongly structure sensitive with particles below 5 nm losing their methanation activity. Operando X-ray diffraction and X-ray absorption spectroscopy results showed that significant oxidation or restructuring, which could be responsible for the observed differences in CO2 hydrogenation rates, was absent. Instead, the decreased methanation activity and the related higher CO selectivity on small nanoparticles was linked to a lower availability of step edges that are active for CO dissociation. Operando infrared spectroscopy coupled with (isotopic) transient experiments revealed the dynamics of surface species on the Ni surface during CO2 hydrogenation and demonstrated that direct dissociation of CO2 to CO is followed by the conversion of strongly bonded carbonyls to CH4. These findings provide essential insights into the much debated structure sensitivity of CO2 hydrogenation reactions and are key for the knowledge-driven design of highly active and selective catalysts.

Squalene is selectively and entirely converted into squalane over the spherical sol-gel-entrapped Pd catalyst SiliaCat Pd(0) under solvent-free and mild reaction conditions of 3 bar H2 and 70 °C. The catalyst was reused successfully in eight consecutive cycles, with palladium leaching values <2 ppm, opening the route to sustainable and less-expensive hydrogenation of phytosqualene with important sustainability consequences.

The conversion of CO2 by renewable power-generated hydrogen is a promising approach to a sustainable production of long-chain olefins (C4+=) which are currently produced from petroleum resources. The decentralized small-scale electrolysis for hydrogen generation requires the operation of CO2 hydrogenation in ambient-pressure units to match the manufacturing scales and flexible on-demand production. Herein, we report a Cu-Fe catalyst which is operated under ambient pressure with comparable C4+= selectivity (66.9%) to that of the state-of-the-art catalysts (66.8%) optimized under high pressure (35 bar). The catalyst is composed of copper, iron oxides, and iron carbides. Iron oxides enable reverse-water-gas-shift to produce CO. The synergy of carbide path over iron carbides and CO insertion path over interfacial sites between copper and iron carbides leads to efficient C-C coupling into C4+=. This work contributes to the development of small-scale low-pressure devices for CO2 hydrogenation compatible with sustainable hydrogen production.

Chemoselectivity is a cornerstone of catalysis, permitting the targeted modification of specific functional groups within complex starting materials. Here we elucidate key structural and electronic factors controlling the liquid phase hydrogenation of cinnamaldehyde and related benzylic aldehydes over Pt nanoparticles. Mechanistic insight from kinetic mapping reveals cinnamaldehyde hydrogenation is structure-insensitive over metallic platinum, proceeding with a common Turnover Frequency independent of precursor, particle size or support architecture. In contrast, selectivity to the desired cinnamyl alcohol product is highly structure sensitive, with large nanoparticles and high hydrogen pressures favoring C = O over C = C hydrogenation, attributed to molecular surface crowding and suppression of sterically-demanding adsorption modes. In situ vibrational spectroscopies highlight the role of support polarity in enhancing C = O hydrogenation (through cinnamaldehyde reorientation), a general phenomenon extending to alkyl-substituted benzaldehydes. Tuning nanoparticle size and support polarity affords a flexible means to control the chemoselective hydrogenation of aromatic aldehydes.

Outer-sphere radical hydrogenation of olefins proceeds via stepwise hydrogen atom transfer (HAT) from transition metal hydride species to the substrate. Typical catalysts exhibit M-H bonds that are either too weak to efficiently activate H2 or too strong to reduce unactivated olefins. This contribution evaluates an alternative approach, that starts from a square-planar cobalt(II) hydride complex. Photoactivation results in Co-H bond homolysis. The three-coordinate cobalt(I) photoproduct binds H2 to give a dihydrogen complex, which is a strong hydrogen atom donor, enabling the stepwise hydrogenation of both styrenes and unactivated aliphatic olefins with H2 via HAT.

Titanium dioxide is the only known material that can enable gas-phase CO2 photocatalysis in its anatase and rutile polymorphic forms. Materials engineering of polymorphism provides a useful strategy for optimizing the performance metrics of a photocatalyst. In this paper, it is shown that the less well known rhombohedral polymorph of indium sesquioxide, like its well-documented cubic polymorph, is a CO2 hydrogenation photocatalyst for the production of CH3OH and CO. Significantly, the rhombohedral polymorph exhibits higher activity, superior stability and improved selectivity towards CH3OH over CO. These gains in catalyst performance originate in the enhanced acidity and basicity of surface frustrated Lewis pairs in the rhombohedral form.

The mechanism of CO hydrogenation to CH4 at 260 °C on a cobalt catalyst is investigated using steady-state isotopic transient kinetic analysis (SSITKA) and backward and forward chemical transient kinetic analysis (CTKA). The dependence of CH x residence time is determined by 12CO/H2 → 13CO/H2 SSITKA as a function of the CO and H2 partial pressure and shows that the CH4 formation rate is mainly controlled by CH x hydrogenation rather than CO dissociation. Backward CO/H2 → H2 CTKA emphasizes the importance of H coverage on the slow CH x hydrogenation step. The H coverage strongly depends on the CO coverage, which is directly related to CO partial pressure. Combining SSITKA and backward CTKA allows determining that the amount of additional CH4 obtained during CTKA is nearly equal to the amount of CO adsorbed to the cobalt surface. Thus, under the given conditions overall barrier for CO hydrogenation to CH4 under methanation condition is lower than the CO adsorption energy. Forward CTKA measurements reveal that O hydrogenation to H2O is also a relatively slow step compared to CO dissociation. The combined transient kinetic data are used to fit an explicit microkinetic model for the methanation reaction. The mechanism involving direct CO dissociation represents the data better than a mechanism in which H-assisted CO dissociation is assumed. Microkinetics simulations based on the fitted parameters confirms that under methanation conditions the overall CO consumption rate is mainly controlled by C hydrogenation and to a smaller degree by O hydrogenation and CO dissociation. These simulations are also used to explore the influence of CO and H2 partial pressure on possible rate-controlling steps.

Unsupported Ni-Mo sulfides have been hydrothermally synthesized and purified by HCl leaching to remove Ni sulfides. Unblocking of active sites by leaching significantly increases the catalytic activity for dibenzothiophene hydrodesulfurization. The site-specific rates of both direct (hydrogenolytic) and hydrogenative desulfurization routes on these active sites that consist of coordinatively unsaturated Ni and sulfhydryl groups were identical for all unsupported sulfides. The hydrogenative desulfurization rates were more than an order of magnitude higher on unsupported Ni-Mo sulfides than on Al2O3-supported catalysts, while they were similar for the direct (hydrogenolytic) desulfurization. The higher activity is concluded to be caused by the lower average electronegativity, i.e., higher base strength and polarity, of Ni-Mo sulfides in the absence of the alumina support and the modified adsorption of reactants enabled by multilayer stacking. Beyond the specific catalytic reaction, the synthesis strategy points to promising scalable routes to sulfide materials broadly applied in hydrogenation and hydrotreating.

An efficient one-pot microwave-assisted hydrogenation of codeine was achieved in aqueous solution. This technique is simple, fast, environmentally friendly, and highly efficient. Structure of produced dihydrocodeine was approved by using FT-IR, (1)H NMR, (13)C NMR, EIMS, and elemental analysis technique. Its purity analysis was performed by using HPLC and assay analysis was performed by using potentiometric titration methods.

Selective hydrogenation of vegetable oils is a significant step in the synthesis of several precursors for the preparation of bioplastics and biodiesel. In this work, a commercial Lindlar catalyst (palladium on calcium carbonate; poisoned with lead) was used as an efficient catalyst in the selective partial hydrogenation of canola and sunflower oils. Different operating conditions (pressure, temperature, and catalyst amount) were tested, and results were achieved by gas chromatography analysis of methyl esters obtained by the transesterification of the triglycerides. The optimized reaction conditions (0.4 MPa, 180 °C, 4 mgcatalyst/mLoil) were determined for the hydrogenation of linoleic acid (C18:2) and linolenic acid (C18:3) with 84.6 and 90.1% of conversion, respectively, into 88.4% relative percentage of oleic acid (C18:1) with low formation of C18:0 (stearic), below 10%, with stability of the catalyst during several cycles with maximum C18:1 relative percentage ranging between 86.6 and 80.7%.

The study of metal phosphide catalysts for organic synthesis is rare. We present, for the first time, a well-defined nano-cobalt phosphide (nano-Co2P) that can serve as a new class of catalysts for the hydrogenation of nitriles to primary amines. While earth-abundant metal catalysts for nitrile hydrogenation generally suffer from air-instability (pyrophoricity), low activity and the need for harsh reaction conditions, nano-Co2P shows both air-stability and remarkably high activity for the hydrogenation of valeronitrile with an excellent turnover number exceeding 58000, which is over 20- to 500-fold greater than that of those previously reported. Moreover, nano-Co2P efficiently promotes the hydrogenation of a wide range of nitriles, which include di- and tetra-nitriles, to the corresponding primary amines even under just 1 bar of H2 pressure, far milder than the conventional reaction conditions. Detailed spectroscopic studies reveal that the high performance of nano-Co2P is attributed to its air-stable metallic nature and the increase of the d-electron density of Co near the Fermi level by the phosphidation of Co, which thus leads to the accelerated activation of both nitrile and H2. Such a phosphidation provides a promising method for the design of an advanced catalyst with high activity and stability in highly efficient and environmentally benign hydrogenations.

Transition metal dichalcogenides (TMDs) are well known catalysts as both bulk and nanoscale materials. Two-dimensional (2-D) TMDs, which contain single- and few-layer nanosheets, are increasingly studied as catalytic materials because of their unique thickness-dependent properties and high surface areas. Here, colloidal 2H-WS2 nanostructures are used as a model 2-D TMD system to understand how high catalytic activity and selectivity can be achieved for useful organic transformations. Free-standing, colloidal 2H-WS2 nanostructures containing few-layer nanosheets are shown to catalyze the selective hydrogenation of a broad scope of substituted nitroarenes to their corresponding aniline derivatives in the presence of other reducible functional groups. Microscopic and computational studies reveal the important roles of sulfur vacancy-rich basal planes and tungsten-terminated edges, which are more abundant in nanostructured 2-D materials than in their bulk counterparts, in enabling the functional group selectivity. At tungsten-terminated edges and on regions of the basal planes having high concentrations of sulfur vacancies, vertical adsorption of the nitroarene is favored, thus facilitating hydrogen transfer exclusively to the nitro group due to geometric effects. At lower sulfur vacancy concentrations on the basal planes, parallel adsorption of the nitroarene is favored, and the nitro group is selectively hydrogenated due to a lower kinetic barrier. These mechanistic insights reveal how the various defect structures and configurations on 2-D TMD nanostructures facilitate functional group selectivity through distinct mechanisms that depend upon the adsorption geometry, which may have important implications for the design of new and enhanced 2-D catalytic materials across a potentially broad scope of reactions.

The control of product distribution in a multistep catalytic selective hydrogenation reaction is challenging. For instance, the deep hydrogenation of dimethyl oxalate (DMO) is inclined to proceed over Cu/SiO2 catalysts because of inevitable coexistence of Cu+ and Cu0, leading to hard acquisition of the preliminary hydrogenation product, methyl glycolate (MG). Here, the oriented DMO hydrogenation into MG is achieved over the sputtering (SP) Cu/SiO2 catalysts with a selectivity of more than 87% via freezing Cu in a zero-valence state. Our density functional theory calculation results revealed that Cu0 is the active site of the preliminary hydrogenation step, selectively converting DMO to MG via •H addition, while Cu+ is a key factor for deep hydrogenation. The prominent Coster-Kronig transition enhancement is observed over SP-Cu/SiO2 from Auger spectra, indicating that the electron density of inner shells in Cu atoms is enhanced by high-energy argon plasma bombardment during the SP process. Thus, the "penetration effect" of outermost electrons could also be enhanced, making these Cu nanoparticles exhibit high oxidation resistance ability and present noble metal-like behaviors as Au or Ag. Therefore, the regulation of Cu chemical properties by changing the electron structure is a feasible strategy to control the hydrogenation products, inspiring the rational design of selective hydrogenation catalysts.

Colloidal Pd nanoparticles capped with octanethiolate ligands have previously shown an excellent selectivity toward the mono-hydrogenation of both isolated and conjugated dienes to internal alkenes. This paper reports an efficient stereoselective mono-hydrogenation of cumulated dienes (allenes) to either Z or E olefinic isomers, depending on the substitution pattern around C=C bonds. Kinetic studies indicate that the reaction progresses through the hydrogenation of less hindered C=C bonds to produce internal Z olefinic isomers. In the cases of di-substitued olefinic products, this initial hydrogenation step is followed by the subsequent isomerization of Z to E isomers. In contrast, the slow isomerization of Z to E isomers for tri-substituted olefinic products results in the preservation of Z stereochemistry. The high selectivity of Pd nanoparticles averting an additional hydrogenation is steered from the controlled electronic and geometric properties of the Pd surface, which are the result of thiolate-induced partial poisoning and surface crowding, respectively. The high activity of colloidal Pd nanoparticle catalysts allows the reactions to be completed at room temperature and atmospheric pressure.

The hydrogenation of metal nanoparticles provides a pathway toward tuning their combustion characteristics. Metal hydrides have been employed as solid-fuel additives for rocket propellants, pyrotechnics, and explosives. Gas generation during combustion is beneficial to prevent aggregation and sintering of particles, enabling a more complete fuel utilization. Here, we discuss a novel approach for the synthesis of magnesium hydride nanoparticles based on a two-step aerosol process. Mg particles are first nucleated and grown via thermal evaporation, followed immediately by in-flight exposure to a hydrogen-rich low-temperature plasma. During the second step, atomic hydrogen generated by the plasma rapidly diffuses into the Mg lattice, forming particles with a significant fraction of MgH2. We find that hydrogenated Mg nanoparticles have an ignition temperature that is reduced by ∼200 °C when combusted with potassium perchlorate as an oxidizer, compared to the non-hydrogenated Mg material. This is due to the release of hydrogen from the fuel, jumpstarting its combustion. In addition, characterization of the plasma processes suggests that a careful balance between the dissociation of molecular hydrogen and heating of the nanoparticles must be achieved to avoid hydrogen desorption during production and achieve a significant degree of hydrogenation.

Parahydrogen (pH2 ) induced polarization (PHIP) is a unique method that is used in analytical chemistry to elucidate catalytic hydrogenation pathways and to increase the signal of small metabolites in MRI and NMR. PHIP is based on adding or exchanging at least one pH2 molecule with a target molecule. Thus, the spin order available for hyperpolarization is often limited to that of one pH2 molecule. To break this limit, we investigated the addition of multiple pH2 molecules to one precursor. We studied the feasibility of the simultaneous hydrogenation of three arms of trivinyl orthoacetate (TVOA) intending to obtain hyperpolarized acetate. It was found that semihydrogenated TVOA underwent a fast decomposition accompanied by several minor reactions including an exchange of geminal methylene protons of a vinyl ester with pH2 . The study shows that multiple vinyl ester groups are not suitable for a fast and clean (without any side products) hydrogenation and hyperpolarization that is desired in biochemical applications.

The selection of experimental conditions leading to a reasonable yield is an important and essential element for the automated development of a synthesis plan and the subsequent synthesis of the target compound. The classical QSPR approach, requiring one-to-one correspondence between chemical structure and a target property, can be used for optimal reaction conditions prediction only on a limited scale when only one condition component (e.g., catalyst or solvent) is considered. However, a particular reaction can proceed under several different conditions. In this paper, we describe the Likelihood Ranking Model representing an artificial neural network that outputs a list of different conditions ranked according to their suitability to a given chemical transformation. Benchmarking calculations demonstrated that our model outperformed some popular approaches to the theoretical assessment of reaction conditions, such as k Nearest Neighbors, and a recurrent artificial neural network performance prediction of condition components (reagents, solvents, catalysts, and temperature). The ability of the Likelihood Ranking model trained on a hydrogenation reactions dataset, (~42,000 reactions) from Reaxys® database, to propose conditions that led to the desired product was validated experimentally on a set of three reactions with rich selectivity issues.

Catalytic hydrogenation is an important process used for the production of everything from foods to fuels. Current heterogeneous implementations of this process utilize metals as the active species. Until recently, catalytic heterogeneous hydrogenation over a metal-free solid was unknown; implementation of such a system would eliminate the health, environmental, and economic concerns associated with metal-based catalysts. Here, we report good hydrogenation rates and yields for a metal-free heterogeneous hydrogenation catalyst as well as its unique hydrogenation mechanism. Catalytic hydrogenation of olefins was achieved over defect-laden h-BN (dh-BN) in a reactor designed to maximize the defects in h-BN sheets. Good yields (>90%) and turnover frequencies (6 × 10-5-4 × 10-3) were obtained for the hydrogenation of propene, cyclohexene, 1,1-diphenylethene, (E)- and (Z)-1,2-diphenylethene, octadecene, and benzylideneacetophenone. Temperature-programmed desorption of ethene over processed h-BN indicates the formation of a highly defective structure. Solid-state NMR (SSNMR) measurements of dh-BN with high and low propene surface coverages show four different binding modes. The introduction of defects into h-BN creates regions of electronic deficiency and excess. Density functional theory calculations show that both the alkene and hydrogen-bond order are reduced over four specific defects: boron substitution for nitrogen (BN), vacancies (VB and VN), and Stone-Wales defects. SSNMR and binding-energy calculations show that VN are most likely the catalytically active sites. This work shows that catalytic sites can be introduced into a material previously thought to be catalytically inactive through the production of defects.