Mild Hydrogenation Research Articles

Al–Cu–Fe–Ni–Ti high entropy alloy nanoparticles as new catalyst for hydrogen sorption in MgH2

The earth's abundance of magnesium hydride (MgH2), along with its favorable qualities like high capacity, excellent reversibility, and cost-effectiveness under mild hydrogenation conditions, make it a potential material for hydrogen storage. Its practical applicability is limited by unfavorable thermodynamics and kinetics, despite these advantages. In this work, we investigate the use of a leached form of the mechanically alloyed high entropy alloy (HEA) Al–Cu–Fe–Ni–Ti as a catalyst to improve the hydrogen storage capabilities of MgH2. The onset desorption temperature of MgH2 is significantly reduced from 360 °C (for as-received MgH2) to 200 °C when catalyzed by the previously stated HEA catalyst. In addition, the catalyst exhibits enhanced kinetics, as it can absorb around 6.2 wt. % in just 2.3 min. at 300 °C and 15 atm of hydrogen pressure, and desorb approximately 5.8 wt. % in 3.8 min. When compared to other known catalysts, these results show some of the lowest desorption temperatures for MgH2. Furthermore, MgH2 catalyzed by the leached form of Al–Cu–Fe–Ni–Ti HEA exhibits good cyclic stability for up to 21 cycles, with just a small variation of about ∼0.02 wt. %. A thorough analysis using X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy have been carried out. We suggest a workable catalytic mechanism for the high entropy alloy Al–Cu–Fe–Ni–Ti on MgH2 based on these findings.

Palladium doped PDA-coated hercynite as a highly efficient catalyst for mild hydrogenation of nitroareness

Hercynite magnetic nanoparticles were produced through the co-precipitation of ferrous and aluminum cations. The surface of hercynite was respectively coated with silica, 2,4,6-trichloro-1,3,5-triazine, and 1H-pyrazole-3,5-dicarboxylic acid to provide a suitable substrate for Pd(II) loading, furnishing Pd@Her-TCT-PDA. Subsequently, the introduced Pd(II) was reduced to Pd(0) using NaBH4. FT-IR, EDS, XRD, TGA, TEM and SEM images were the characteristic methods to prove the success of catalyst synthesis. The SEM image illustrated the particles with a nanosize of 25–50 nm and TEM image confirmed the presence of Pd nanoparticles with sizes lower than 2 nm. EDS elemental analysis of the catalyst proved the existence of Pd, Fe, and Al atoms along with the C, O, N, and Si atoms belong to the heterocyclic moieties. VSM analysis clarified a considerable drop in the magnetic properties of the hercynite core of the final catalyst due to its modified surface. TGA curve demonstrated that Pd@Her-TCT-PDA contains 20% organic content, attributed to the anchored heterocyclic ligands. Finally, Pd@Her-TCT-PDA was employed along with NaBH4 as a catalytic system to reduce completely the nitro group of aromatic compounds to their corresponding amines. The recyclability tests showed low drop in the catalytic activity of Pd@Her-TCT-PDA after third run with negligible leaching of Pd NPs.

Inexpensive and mild hydrogenation condition: Raney Ni-catalyzed reduction of alkenes and alkynes using Et3SiH at ambient temperature

The Raney Ni-catalyzed hydrogenation of alkenes and alkynes has been developed. Et3SiH was chosen as the reductant. Substrates with various substituents were reduced at ambient temperature, affording good to excellent yields. No pressure reactor, heating, or inert atmosphere is required and the catalyst can be removed/recycled by simple filtration.

Late-Stage Saturation of Drug Molecules.

The available methods of chemical synthesis have arguably contributed to the prevalence of aromatic rings, such as benzene, toluene, xylene, or pyridine, in modern pharmaceuticals. Many such sp2-carbon-rich fragments are now easy to synthesize using high-quality cross-coupling reactions that click together an ever-expanding menu of commercially available building blocks, but the products are flat and lipophilic, decreasing their odds of becoming marketed drugs. Converting flat aromatic molecules into saturated analogues with a higher fraction of sp3 carbons could improve their medicinal properties and facilitate the invention of safe, efficacious, metabolically stable, and soluble medicines. In this study, we show that aromatic and heteroaromatic drugs can be readily saturated under exceptionally mild rhodium-catalyzed hydrogenation, acid-mediated reduction, or photocatalyzed-hydrogenation conditions, converting sp2 carbon atoms into sp3 carbon atoms and leading to saturated molecules with improved medicinal properties. These methods are productive in diverse pockets of chemical space, producing complex saturated pharmaceuticals bearing a variety of functional groups and three-dimensional architectures. The rhodium-catalyzed method tolerates traces of dimethyl sulfoxide (DMSO) or water, meaning that pharmaceutical compound collections, which are typically stored in wet DMSO, can finally be reformatted for use as substrates for chemical synthesis. This latter application is demonstrated through the late-stage saturation (LSS) of 768 complex and densely functionalized small-molecule drugs.

Mild and selective transfer hydrogenation of biomass-derived furfural to furfuryl alcohol over Cu/ZnO/Al2O3 with methanediol as the hydrogen donor

Water, in the presence of formaldehyde, splitting to generate in situ hydrogen for selective hydrogenation of biomass-derived furfural to furfury alcohol catalyzed by copper-based catalyst under mild conditions.

Mild and Selective Hydrogenation of Unsaturated Compounds Using Mn/Water as a Hydrogen Gas Source.

A mild and highly selective reduction of alkenes and alkynes using Mn/water is described. The highly controlled generation of H2 allows the selective reduction of these compounds in the presence of labile functional groups under mild and environmentally acceptable conditions.

Mild Hydrogenation of 2-Furoic Acid by Pt Nanoparticles Dispersed in a Hierarchical ZSM-5 Zeolite.

Hydrogenation of biobased compounds can add value to platform molecules obtained from biomass refining. Herein, we explore the hydrogenation of 2-furoic acid (2-furancarboxylic acid, FCA), a derivative of furfural, with H2 generated in situ by NaBH4 hydrolysis at ambient conditions. Nearly complete conversion of FCA was obtained with tetrahydrofuroic acid (THFA) and 5-hydroxyvaleric acid (5-HVA) as the only two reaction products over Pt nanoparticles supported on hierarchical ZSM-5. Small Pt nanoparticles (2 to 3 nm) were stabilized by ZSM-5 nanosheets. At an optimized Pt loading, the Pt nanoparticles can catalyze the hydrolysis of NaBH4 and the subsequent hydrogenation of FCA with the assistance of Brønsted acid sites. Nanostructuring ZSM-5 into nanosheets and its acidity contributes to the stability of the dispersed Pt nanoparticles. Deactivation due to NaBO2 deposition on the Pt particles can be countered by a simple washing treatment. Overall, this approach shows the promise of mild hydrogenation of biobased feedstock coupled with NaBH4 hydrolysis.

Hydrogenation of CO2 by a Bifunctional PC(sp3 )P Iridium(III) Pincer Complex Equipped with Tertiary Amine as a Functional Group.

Reversible hydrogen storage in the form of stable and mostly harmless chemical substances such as formic acid (FA) is a cornerstone of a fossil fuels-free economy. In the past, we have reported a primary amine-functionalized bifunctional iridium(III)-PC(sp3 )P pincer complex as a mild and chemoselective catalyst for the additive-free decomposition of neat formic acid. In this manuscript, we report on the successful application of a redesigned complex bearing tertiary amine functionality as a catalyst for mild hydrogenation of CO2 to formic acid. The catalyst demonstrates TON up to 6×104 and TOF up to 1.7×104 h-1 . In addition to the practical value of the catalyst, experimental and computational mechanistic studies provide the rationale for the design of improved next-generation catalysts.

Metal Effect on Cationic [Cp2MH]+ (M = Group 4 and 5)-Mediated CO2 Hydrogenation in the Gas Phase.

Effective CO2 hydrogenation has recently attracted quite some attention for producing more valuable chemical oxygenates (such as methanol, formate) in mild conditions. However, the influence of the metal center on the CO2 activation remains unclear. First, electrospray ionization mass spectrometry (ESI-MS) was employed to explore the direct CO2 hydrogenation to formic acid mediated by [Cp2MH]+ (M = Zr, Hf) in the gas phase at room temperature. The key formate intermediate [Cp2M(O2CH)]+ (M = Zr, Hf) was confirmed by traveling wave ion mobility spectrometry (TWIMS). Second, to gain insights into the metal effect, the CO2 hydrogenation process involving Group 4 (i.e., Ti, Zr, Hf) transition metals was calculated along with Group 5 (i.e., V, Nb, Ta) by density functional theory (DFT) methods. The CO2 insertion process was found to be the rate-limiting step. For [Cp2TiH]+, [Cp2ZrH]+, [Cp2HfH]+, [Cp2VH]+, [Cp2NbH]+, and [Cp2TaH]+, the barriers are +7.7, +6.5, +5.9, +9.2, +8.0, and +6.3 kcal/mol, respectively. [Cp2HfH]+-mediated CO2 hydrogenation occurs the most rapidly, as revealed by MS. According to the orbital analysis on the CO2 insertion transition state, the electron-deficient metal center resulting in a low-lying lowest unoccupied molecular orbital (LUMO) could interact more favorably with the π bond of deformed CO2, which was also consistent with the natural bond orbital (NBO) results. Last but not the least, NBO charges on the metal centers were found to correlate linearly well with the CO2 insertion barriers rather than hydride affinity. Thus, the reactivity of different metal hydride complexes with CO2 to produce a formate could be estimated by the NBO charge on metals. Our findings might provide a series of candidates for the catalyst as well as guidance for catalyst design in mild CO2 hydrogenation.

Generalized Rapid Synthesis of Supported Nanocluster Catalyst for Mild Hydrogenation of Phenol toward KA Oil.

Homogeneous and nanometric metal clusters with unique electronic structures are promising for catalysis, however, common synthesis techniques for metal clusters suffer from large size and even metal nanocrystals attributing to their high surface energy and unsaturated configurations. Herein, a generalized rapid annealing strategy for synthesizing a series of supported metal clusters as superior catalysts is developed. Remarkably, TiO2 supported platinum nanoclusters (Pt NC/TiO2 ) exhibits the excellent catalytic activity to realize phenol hydrogenation under mild conditions. The complete phenol conversion rate and 100% selectivity toward KA oil are achieved in aqueous solution at room temperature and normal pressure. Semi-continuous scale up production of KA oil is successfully performed under mild conditions. Such excellent performance mainly originates from the partial reconstruction of Pt NC/TiO2 in aqueous phenol solution. Considering that the phenol can be produced from lignin, this study underpins a facile, sustainable, and economical route to synthesize nylon from biomass.

A High‐Valent Ru−PCP Pincer Catalyst for the Hydrogenation of Organic Carbonates

AbstractIn this communication, we report on the successful application of a high‐valent RuIV bifunctional catalyst (1) for mild hydrogenation of cyclic and acyclic carbonates. Our experimental and theoretical studies suggest that the hydrogenation mechanism is operated by an unusual formally zwitterionic RuIV complex. According to our hypothesis, the positively charged high‐valent metal center is responsible for stronger hydrogen coordination. On the other hand, the proximate negatively charged ligand site facilitates heterolytic H2 bond activation, which leads to efficient catalysis.

Glucose-derived zirconium-containing mesoporous composite for efficient catalytic transfer hydrogenation of furfural to furfuryl alcohol

Meerwein-Ponndorf-Verley (MPV) reaction has been widely acknowledged to be a mild catalytic transfer hydrogenation method for selective reduction of biomass-derived furfural to furfuryl alcohol. Herein zirconium-containing mesoporous composite catalyst was developed through the combination of sol-gel process and soft templating method, in which naturally abundant glucose and F127 triblock copolymer were used as the ligand and pore-forming agent, respectively. The hydroxyl groups in glucose molecules were demonstrated to be coordinated with zirconium ion during hydrolysis-condensation of zirconium precursor, leading to the even dispersion of zirconia nanoparticles in the composite catalyst. The composite catalyst was proven to be highly efficient for catalyzing MPV reduction of furfural with the maximum furfuryl alcohol yield of 93.4% at 180 °C within 180 min in 2-propanol, which served as both solvent and reductant. The composite also showed a good reusability. After five consecutive reaction cycles, furfuryl alcohol yield was slightly reduced from 93.4% to 77.7%, but it could be recovered to 92.8% after the reused composite was regenerated with dilute alkali solution. Batch experiments and systematic characterizations demonstrated that the excellent catalytic performance of composite catalyst was determined by multiple factors mainly including the stronger Lewis acidity, a considerable amount of basic site and the rich mesoporous structure. This study provides a facile strategy to prepare multifunctional composite catalysts using naturally abundant carbohydrates as the feedstocks for lignocellulosic biorefinery.

Formal Nitrene Insertion into the β-Vinyl C-H Bond of Acroleins: Synthesis of Enaminals.

An efficient formal nitrene insertion reaction into the β-vinyl C-H bond of acroleins with an electron-rich organic azide was developed. The reaction protocol can produce secondary enaminals in high yield with a broad substrate scope. In the reaction, acid mediated [3 + 2] cycloaddition of organic azides with an acrolein generated intermediate protonated triazolines, which were selectively decomposed into enaminals with addition of a weakly Brønsted basic reagent such as methanol. The resulting secondary enaminal could be easily reduced into a γ-amino alcohol under mild hydrogenation conditions.

Mild and metal-free Birch-type hydrogenation of (hetero)arenes with boron carbonitride in water

Mild and metal-free Birch-type hydrogenation of (hetero)arenes with boron carbonitride in water

Short, Divergent, and Enantioselective Total Synthesis of Bioactive ent-Pimaranes.

We present the first total synthesis of eight ent-pimaranes via a short and enantioselective route (11-16 steps). Key features of the divergent synthesis are a Sharpless asymmetric dihydroxylation, a Brønsted acid catalyzed cationic bicyclization, and a mild Rh-catalyzed arene hydrogenation for rapid access to a late synthetic branching point. From there on, selective functional group manipulations enable the synthesis of ent-pimaranes bearing different modifications in the A- and C-rings.

Mild and Efficient Heterogeneous Hydrogenation of Nitroarenes Facilitated by a Pyrolytically Activated Dinuclear Ni(II)-Ce(III) Diimine Complex.

We communicate the assembly of a solid, Ce-promoted Ni-based composite that was applied as catalyst for the hydrogenation of nitroarenes to afford the corresponding organic amines. The catalytically active material described herein was obtained through pyrolysis of a SiO2-pellet-supported bimetallic Ni-Ce complex that was readily synthesized prior to use from a MeO-functionalized salen congener, Ni(OAc)2·4 H2O, and Ce(NO3)3·6 H2O. Rewardingly, the requisite ligand for the pertinent solution phase precursor was accessible upon straightforward and time-saving imine condensation of ortho-vanillin with 1,3-diamino-2,2′-dimethylpropane. The introduced catalytic protocol is operationally simple in that the whole reaction set-up is quickly put together on the bench without the need of cumbersome handling in a glovebox or related containment systems. Moreover, the advantageous geometry and compact-sized nature of the used pellets renders the catalyst separation and recycling exceptionally easy.

Fullerenes make copper catalysis better.

Ethylene glycol can be reliably produced by mild hydrogenation of dimethyl oxalate.

Conversion of dimethyl ether to liquid hydrocarbons over Zn-isomorphously substituted HZSM-5

Zinc-isomorphously substituted HZSM-5 (Zn/HZSM-5(iso)) surpasses Zn/HZSM-5(i.e) sample obtained by ion exchange in its catalytic performance in the conversion of a mixture of DME + syngas (in different compositions) to liquid hydrocarbons. The uniform distribution of highly dispersed zinc species over zeolite crystals provides high selectivity of Zn/HZSM-5(iso) to liquid hydrocarbons (90 wt%). New ZnOH+ active sites of medium strength with mild hydrogenation properties explain the low yield of arenes (4.7 wt%) and the high yield of i-alkanes (72.5 wt%). The absence of methanol in the product stream indicates its dehydration to DME, which is known to have a higher reactivity or its participation in the methylation of alkenes to form methyl-substituted alkanes. A larger mesopores volume in Zn/HZSM-5(iso) promotes a lower degree of coke precursors polycondensation. Therefore, this allows the use of mild oxidative regeneration conditions. The Zn/HZSM-5(iso) catalyst retains its efficient and stable operation for 72 h, with high conversion of DME and high selectivity for liquid hydrocarbons. The resulting hydrocarbon mixture can be used as a base component for environmentally friendly fuels.

Facile Fabrication of Durable Biochar/H2-TiO2 for Highly Efficient Solar-Driven Degradation of Enrofloxacin: Properties, Degradation Pathways, and Mechanism.

Widespread application of TiO2 for degradation of antibiotics is restricted by mainly the low photodegradation efficiency under solar irradiation. To expand the application of TiO2, the key factors that should be improved are visible-light response, yield of electrons and holes, and durability. Herein, we report a visible-light responsive and durable sugarcane-bagasse-derived biochar supported hydrogenated TiO2 (HSCB/H2-TiO2) photocatalyst with higher electron production fabricated by a facile one-pot hydrogenation. Mild hydrogenation temperature preserved the lotus-stem-like structure of sugarcane bagasse and gave the photocatalyst great separability. The superior durability of HSCB/H2-TiO2 was demonstrated by 12 rounds of repeated degradation of methylene blue (MB). In addition, the electron paramagnetic resonance (EPR) results demonstrated that the biochar skeleton contains abundant persistent free radicals (PFRs), which can provide excess electrons to form more •O2–. Meanwhile, radical quenching experiment and EPR radical trapping results also revealed that •O2– was the most dominant species for enrofloxacin (ENR) degradation. Thus, the as-fabricated photocatalyst shows excellent solar-driven degradation of ENR, and 95.6% of ENR was degraded in 180 min under simulated solar irradiation. Possible ENR degradation pathways and mechanism are also proposed based on the identified intermediates.

Mild hydrogenation pretreatment of FCC slurry oil for high-value-added utilization: Exploitable high-boiling components and carbonization discrepancy

In response to the enormous market demand for high-value-added carbonaceous materials and the urgent requirement of energy conservation and emission reduction, FCC slurry oil (SO) has drawn widespread attention in the preparation of these kinds of carbonaceous materials due to its abundant aromatic hydrocarbon contents. Distillation can be utilized as a pretreatment to efficiently remove the quinoline insoluble and other undesirable components in SO before carbonization. However, the distillate depth and yield are greatly restricted by the conspicuous coking phenomenon during thermal effect in the distillation. Mild hydrogenation coupled with distillation were adopted as the pretreatments before carbonization and effects of the hydrogenation on the distillation process were studied. Besides, transform patterns for the properties of sub-fractions in specimen before and after hydrogenation and resulted variations in carbonization performances were then systematically analyzed. Through hydrogenation, the distillation depth of hydrotreated SO (HSO) could be greatly improved to 530 °C with no significant coking phenomenon and the distillation yield was increased dramatically (from 38.4 wt% to 68.1 wt%). Especially, partial super high-boiling (above 530 °C) components in SO could be transformed into naphthenoaromatic structures by hydrogenation and acquired through distillation for further utilizations. Using anthracene as chemical probe, the hydrogen-donating abilities (HDAs) of specimens were detected, and results indicated the amounts of transferable hydrogen in HSO low-boiling and high-boiling sub-fractions were greatly increased compared with that of SO, which would provide the specimen with stronger stability in the thermal treatment and restrain the rapid coking. The carbonization performance varied with the properties of sub-fractions and a section of high-boiling components in SO was discovered to be exploitable through hydrogenation and demonstrated to be beneficial in the preparation of needle coke.