Synthesis, Characterization, and Catalytic Application of Colloidal and Supported Manganese Nanoparticles.

Colloidal and supported manganese nanoparticles were synthesized following an organometallic approach and applied in the catalytic transfer hydrogenation (CTH) of aldehydes and ketones. Reaction parameters for the preparation of colloidal nanoparticles (NPs) were optimized to yield small (2-2.5 nm) and well-dispersed NPs. Manganese NPs were further immobilized on an imidazolium-based supported ionic phase (SILP) and characterized to evaluate NP size, metal loading, and oxidation states. Oxidation of the Mn NPs by the support was observed resulting in an average formal oxidation state of +2.5. The MnOx@SILP material showed promising performance in the CTH of aldehydes and ketones using 2-propanol as a hydrogen donor, outperforming previously reported Mn NPs-based CTH catalysts in terms of metal loading-normalized turnover numbers. Interestingly, MnOx@SILP were found to lose activity upon air exposure, which correlates with an additional increase in the average oxidation state of Mn as revealed by X-ray absorption spectroscopic studies.

Decarboxylation and Tandem Reduction/Decarboxylation Pathways to Substituted Phenols from Aromatic Carboxylic Acids Using Bimetallic Nanoparticles on Supported Ionic Liquid Phases as Multifunctional Catalysts.

Valuable substituted phenols are accessible via the selective decarboxylation of hydroxybenzoic acid derivatives using multifunctional catalysts composed of bimetallic iron-ruthenium nanoparticles immobilized on an amine-functionalized supported ionic liquid phase (Fe25Ru75@SILP+IL-NEt2). The individual components of the catalytic system are assembled using a molecular approach to bring metal and amine sites into close contact on the support material, providing high stability and high decarboxylation activity. Operating under a hydrogen atmosphere was found to be essential to achieve high selectivity and yields. As the catalyst materials enable also the selective hydrogenation and hydrodeoxygenation of various additional functional groups (i.e., formyl, acyl, and nitro substituents), direct access to the corresponding phenols can be achieved via integrated tandem reactions. The approach opens versatile synthetic pathways for the production of valuable phenols from a wide range of readily available substrates, including compounds derived from lignocellulosic biomass.

A Simple and Versatile Approach for the Low-Temperature Synthesis of Transition Metal Phosphide Nanoparticles from Metal Chloride Complexes and P(SiMe3 )3.

Metal chloride complexes react with tris(trimethylsilyl)phosphine under mild condition to produce metal phosphide (TMP) nanoparticles (NPs), and chlorotrimethylsilane as a byproduct. The formation of Si-Cl bonds that are stronger than the starting M-Cl bonds acts as a driving force for the reaction. The potential of this strategy is illustrated through the preparation of ruthenium phosphide NPs using [RuCl2 (cymene)] and tris(trimethylsilyl)phosphine at 35 °C. Characterization with a combination of techniques including electron microscopy (EM), X-ray absorption spectroscopy (XAS), and solid-state nuclear magnetic resonance (NMR) spectroscopy, evidences the formation of small (diameter of 1.3 nm) and amorphous NPs with an overall Ru50 P50 composition. Interestingly, these NPs can be easily immobilized on functional support materials, which is of great interest for potential applications in catalysis and electrocatalysis. Mo50 P50 and Co50 P50 NPs can also be synthesized following the same strategy. This approach is simple and versatile and paves the way toward the preparation of a wide range of transition metal phosphide nanoparticles under mild reaction conditions.

Adaptive Catalysts for the Selective Hydrogenation of Bicyclic Heteroaromatics using Ruthenium Nanoparticles on a CO2 -Responsive Support.

Ruthenium nanoparticles (NPs) immobilized on an amine-functionalized polymer-grafted silica support act as adaptive catalysts for the hydrogenation of bicyclic heteroaromatics. Whereas full hydrogenation of benzofuran and quinoline derivatives is achieved under pure H2 , introducing CO2 into the H2 gas phase leads to an effective shutdown of the arene hydrogenation while preserving the activity for the hydrogenation of the heteroaromatic part. The selectivity switch originates from the generation of ammonium formate species on the surface of the materials by catalytic hydrogenation of CO2 . The CO2 hydrogenation is fully reversible, resulting in a robust and rapid switch between the two states of the catalyst adapting its performance in response to the feed gas composition. A variety of benzofuran and quinoline derivatives were hydrogenated to fully or partially saturated products in high selectivity and yields simply by altering the composition of the feed gas from H2 to H2 /CO2 . The adaptive catalytic system thus provides controlled access to valuable products using a single catalyst rather than two specific and distinct catalysts with static reactivity.

Adaptive Catalytic Systems for Chemical Energy Conversion.

The rapidly growing importance of green hydrogen and renewable carbon resources as essential feedstocks for sustainable chemical value chains opens room for disruptive innovations regarding chemical production processes. The fluctuation and variability associated with non-fossil energy and raw material supply holds many challenges for catalysts to cope with the resulting dynamics. However, many new opportunities also arise once catalyst design starts to aim at performance that is "adaptive" rather than "task-specific". In this Scientific Perspective, we propose to define adaptivity in catalysis on the basis of three essential properties that are reversibility, rapidity, and robustness (R3 rule). Promising design strategies and selected examples are described to substantiate the scientific concept and to highlight its potential for chemical energy conversion.

Catalytic Hydrogenation of CO2 to Formate Using Ruthenium Nanoparticles Immobilized on Supported Ionic Liquid Phases.

Ruthenium nanoparticles (NPs) immobilized on imidazolium-based supported ionic liquid phases (Ru@SILP) act as effective heterogeneous catalysts for the hydrogenation of carbon dioxide (CO2 ) to formate in a mixture of water and triethylamine (NEt3 ). The structure of the imidazolium-based molecular modifiers is varied systematically regarding side chain functionality (neutral, basic, and acidic) and anion to assess the influence of the IL-type environment on the NPs synthesis and catalytic properties. The resulting Ru@SILP materials contain well-dispersed Ru NPs with diameters in the range 0.8-2.9 nm that are found 2 to 10 times more active for CO2 hydrogenation than a reference Ru@SiO2 catalyst under identical conditions. Introduction of sulfonic acid groups in the IL modifiers results in a greatly increased turnover number (TON) and turnover frequency (TOF) at reduced metal loadings. As a result, excellent productivity with TONs up to 16 100 at an initial TOF of 1430 h-1 can be achieved with the Ru@SILP(SO3 H-OAc) catalyst. H/D exchange and other control experiments suggest an accelerated desorption of the formate species from the Ru NPs promoted by the presence of ammonium sulfonate species on Ru@SILP(SO3 H-X) materials, resulting in enhanced catalyst activity and productivity.

Commercial Cu2 Cr2 O5 Decorated with Iron Carbide Nanoparticles as a Multifunctional Catalyst for Magnetically Induced Continuous-Flow Hydrogenation of Aromatic Ketones.

Copper chromite is decorated with iron carbide nanoparticles, producing a magnetically activatable multifunctional catalytic system. This system (ICNPs@Cu2 Cr2 O5 ) can reduce aromatic ketones to aromatic alcohols when exposed to magnetic induction. Under magnetic excitation, the ICNPs generate locally confined hot spots, selectively activating the Cu2 Cr2 O5 surface while the global temperature remains low (≈80 °C). The catalyst selectively hydrogenates a scope of benzylic and non-benzylic ketones under mild conditions (3 bar H2 , heptane), while ICNPs@Cu2 Cr2 O5 or Cu2 Cr2 O5 are inactive when the same global temperature is adjusted by conventional heating. A flow reactor is presented that allows the use of magnetic induction for continuous-flow hydrogenation at elevated pressure. The excellent catalytic properties of ICNPs@Cu2 Cr2 O5 for the hydrogenation of biomass-derived furfuralacetone are conserved for at least 17 h on stream, demonstrating for the first time the application of a magnetically heated catalyst to a continuously operated hydrogenation reaction in the liquid phase.

Rh NPs Immobilized on Phosphonium- based Supported Ionic Liquid Phases (Rh@SILPs) as Hydrogenation Catalysts.

A series of phosphonium-based supported ionic liquid phases (SILPs) was prepared for the immobilization of Rh nanoparticles (Rh@SILP). The influence of systematic variations in the structure of the ionic liquid-type molecular modifiers (anion, P-alkyl chain length) on the formation and catalytic properties of Rh nanoparticles (NPs) was investigated. Both the nature of the anion and the length of the P-alkyl chain were found to have a strong impact on the morphology of the NPs, ranging from small (1.2-1.7 nm) and well-dispersed NPs to the formation of large NPs (9.9-16.5 nm) and/or aggregates. The catalytic properties of the resulting Rh@SILP materials were explored using the hydrogenation of benzylideneacetone and biomass-derived furfuralacetone as model reactions. The changes in ring and C=O hydrogenation activity as a function of the SILP structure and the Rh NPs size allowed for the selective synthesis of products with distinct molecular functionalities.

Selectivity control in hydrogenation through adaptive catalysis using ruthenium nanoparticles on a CO2-responsive support.

With the advent of renewable carbon resources, multifunctional catalysts are becoming essential to hydrogenate selectively biomass-derived substrates and intermediates. However, the development of adaptive catalytic systems, that is, with reversibly adjustable reactivity, able to cope with the intermittence of renewable resources remains a challenge. Here, we report the preparation of a catalytic system designed to respond adaptively to feed gas composition in hydrogenation reactions. Ruthenium nanoparticles immobilized on amine-functionalized polymer-grafted silica act as active and stable catalysts for the hydrogenation of biomass-derived furfural acetone and related substrates. Hydrogenation of the carbonyl group is selectively switched on or off if pure H2 or a H2/CO2 mixture is used, respectively. The formation of alkylammonium formate species by the catalytic reaction of CO2 and H2 at the amine-functionalized support has been identified as the most likely molecular trigger for the selectivity switch. As this reaction is fully reversible, the catalyst performance responds almost in real time to the feed gas composition.

Metal Nanoparticles Immobilized on Molecularly Modified Surfaces: Versatile Catalytic Systems for Controlled Hydrogenation and Hydrogenolysis.

The synthesis and use of supported metal nanoparticle catalysts have a long-standing tradition in catalysis, typically associated with the field of heterogeneous catalysis. More recently, the development and understanding of catalytic systems composed of metal nanoparticles (NPs) that are synthesized from organometallic precursors on molecularly modified surfaces (MMSs) have opened a conceptually new approach to the design of multifunctional catalysts (NPs@MMS). These complex yet fascinating materials bridge molecular ("homogeneous") and material ("heterogeneous") approaches to catalysis and provide access to catalytic systems with tailor-made reactivity through judicious combinations of supports, molecular modifiers, and nanoparticle precursors. A particularly promising field of application is the controlled activation and transfer of dihydrogen, enabling highly selective hydrogenation and hydrogenolysis reactions as relevant for the conversion of biogenic feedstocks and platform chemicals as well as for novel synthetic pathways to fine chemicals and even pharmaceuticals. Consequently, the topic offers an emerging field for interdisciplinary research activities involving organometallic chemists, material scientists, synthetic organic chemists, and catalysis experts.This Account will provide a brief overview of the historical background and cover examples from the most recent developments in the field. A coherent account on the methodological and experimental basis will be given from the long-standing experience in our laboratories. MMSs are widely accessible via chemisorption and physisorption methods for the generation of stable molecular environments on solid surfaces, whereby a special emphasis is given here to ionic liquid-type molecules as modifiers (supported ionic liquid phases, SILPs) and silica as support material. Metal nanoparticles are synthesized following an organometallic approach, allowing the controlled formation of small and uniformly dispersed monometallic or multimetallic NPs in defined composition. A combination of techniques from molecular and material characterization provides a detailed insight into the structure of the resulting materials across various scales (electron microscopy, solid-state NMR, XPS, XAS, etc.).The molecular functionalities grafted on the silica surface have a pronounced influence on the formation, stabilization, and reactivity of the NPs. The complementary and synergistic fine-tuning of the metal and its molecular environment in NPs@MMSs allow in particular the control of the activation of hydrogen and its transfer to substrates. Monometallic (Ru, Rh, Pd) monofunctional NPs@MMSs possess excellent activities for the hydrogenation of alkenes, alkynes, and arenes for which a nonpolarized (homolytic) activation of H2 is predominant. The incorporation of 3d metals in noble metal NPs to give bimetallic (FeRu, CoRh, etc.) monofunctional NPs@MMSs favors a more polarized H2 activation and thus its transfer to the C═O bond, while at the same time preventing the arrangement of noble metal atoms necessary for ring hydrogenation. The incorporation of reactive functionalities, such as, for example, a -SO3H moiety on NPs@MMSs, results in bifunctional catalysts enabling the heterolytic cleavage corresponding to a formal H-/H+ transfer. Consequently, such catalysts possess excellent deoxygenation activity with strong synergistic effects arising from an intimate contact between the nanoparticles and the molecular functionality.While many more efforts are still required to explore, control, and understand the chemistry of NPs@MMS catalysts fully, the currently available examples already highlight the large potential of this approach for the rational design of multifunctional catalytic systems.

Organometallic Synthesis of Bimetallic Cobalt-Rhodium Nanoparticles in Supported Ionic Liquid Phases (Cox Rh100- x @SILP) as Catalysts for the Selective Hydrogenation of Multifunctional Aromatic Substrates.

The synthesis, characterization, and catalytic properties of bimetallic cobalt-rhodium nanoparticles of defined Co:Rh ratios immobilized in an imidazolium-based supported ionic liquid phase (Cox Rh100- x @SILP) are described. Following an organometallic approach, precise control of the Co:Rh ratios is accomplished. Electron microscopy and X-ray absorption spectroscopy confirm the formation of small, well-dispersed, and homogeneously alloyed zero-valent bimetallic nanoparticles in all investigated materials. Benzylideneacetone and various bicyclic heteroaromatics are used as chemical probes to investigate the hydrogenation performances of the Cox Rh100- x @SILP materials. The Co:Rh ratio of the nanoparticles is found to have a critical influence on observed activity and selectivity, with clear synergistic effects arising from the combination of the noble metal and its 3d congener. In particular, the ability of Cox Rh100- x @SILP catalysts to hydrogenate 6-membered aromatic rings is found to experience a remarkable sharp switch in a narrow composition range between Co25 Rh75 (full ring hydrogenation) and Co30 Rh70 (no ring hydrogenation).

Molecular Control of the Catalytic Properties of Rhodium Nanoparticles in Supported Ionic Liquid Phase (SILP) Systems.

Rhodium nanoparticles (NPs) immobilized on imidazolium-based supported ionic liquid phases (Rh@SILP) act as effective catalysts for the hydrogenation of biomass-derived furfuralacetone. The structure of ionic liquid-type (IL) molecular modifiers was systematically varied regarding spacer, side chain, and anion to assess the influence on the NP synthesis and their catalytic properties. Well-dispersed Rh NPs with diameters in the range of 0.6-2.0 nm were formed on all SILP materials, whereby the actual size was dependent significantly on the IL structure. The resulting variations in catalytic activity for hydrogenation of the C=O moiety in furfuralacetone allowed control of the product selectivity to obtain either the saturated alcohol or the ketone in high yield. Experiments conducted under batch and continuous flow conditions demonstrated that Rh NPs immobilized on SILPs with suitable IL structures are more active and much more stable than Rh@SiO2 catalyst synthesized on unmodified silica.

Selective hydrodeoxygenation of hydroxyacetophenones to ethyl-substituted phenol derivatives using a FeRu@SILP catalyst.

The selective hydrodeoxygenation of hydroxyacetophenone derivatives is achieved opening a versatile pathway for the production of valuable substituted ethylphenols from readily available substrates. Bimetallic iron ruthenium nanoparticles immobilized on an imidazolium-based supported ionic liquid phase (Fe25Ru75@SILP) show high activity and stability for a broad range of substrates without acidic co-catalysts.

Selective Hydrogenation and Hydrodeoxygenation of Aromatic Ketones to Cyclohexane Derivatives Using a Rh@SILP Catalyst.

Rhodium nanoparticles immobilized on an acid-free triphenylphosphonium-based supported ionic liquid phase (Rh@SILP(Ph3 -P-NTf2 )) enabled the selective hydrogenation and hydrodeoxygenation of aromatic ketones. The flexible molecular approach used to assemble the individual catalyst components (SiO2 , ionic liquid, nanoparticles) led to outstanding catalytic properties. In particular, intimate contact between the nanoparticles and the phosphonium ionic liquid is required for the deoxygenation reactivity. The Rh@SILP(Ph3 -P-NTf2 ) catalyst was active for the hydrodeoxygenation of benzylic ketones under mild conditions, and the product distribution for non-benzylic ketones was controlled with high selectivity between the hydrogenated (alcohol) and hydrodeoxygenated (alkane) products by adjusting the reaction temperature. The versatile Rh@SILP(Ph3 -P-NTf2 ) catalyst opens the way to the production of a wide range of high-value cyclohexane derivatives by the hydrogenation and/or hydrodeoxygenation of Friedel-Crafts acylation products and lignin-derived aromatic ketones.

Water-Dispersible and Biocompatible Iron Carbide Nanoparticles with High Specific Absorption Rate.

Magnetic nanoparticles are important tools for biomedicine, where they serve as versatile multifunctional instruments for a wide range of applications. Among these applications, magnetic hyperthermia is of special interest for the destruction of tumors and triggering of drug delivery. However, many applications of magnetic nanoparticles require high-quality magnetic nanoparticles displaying high specific absorption rates (SARs), which remains a challenge today. We report here the functionalization and stabilization in aqueous media of highly magnetic 15 nm iron carbide nanoparticles featuring excellent heating power through magnetic induction. The challenge of achieving water solubility and colloidal stability was addressed by designing and using specific dopamine-based ligands. The resulting nanoparticles were completely stable for several months in water, phosphate, phosphate-buffered saline, and serum-containing media. Iron carbide nanoparticles displayed high SARs in water and viscous media (water/glycerol mixtures), even after extended exposition to water and oxygen (SAR up to 1000 W·g-1 in water at 100 kHz, 47 mT). The cytotoxicity and cellular uptake of iron carbide nanoparticles could be easily tuned and were highly dependent on the chemical structure of the ligands used.

Bimetallic Nanoparticles in Supported Ionic Liquid Phases as Multifunctional Catalysts for the Selective Hydrodeoxygenation of Aromatic Substrates.

Bimetallic iron-ruthenium nanoparticles embedded in an acidic supported ionic liquid phase (FeRu@SILP+IL-SO3 H) act as multifunctional catalysts for the selective hydrodeoxygenation of carbonyl groups in aromatic substrates. The catalyst material is assembled systematically from molecular components to combine the acid and metal sites that allow hydrogenolysis of the C=O bonds without hydrogenation of the aromatic ring. The resulting materials possess high activity and stability for the catalytic hydrodeoxygenation of C=O groups to CH2 units in a variety of substituted aromatic ketones and, hence, provide an effective and benign alternative to traditional Clemmensen and Wolff-Kishner reductions, which require stoichiometric reagents. The molecular design of the FeRu@SILP+IL-SO3 H materials opens a general approach to multifunctional catalytic systems (MM'@SILP+IL-func).

Magnetically Induced Continuous CO2 Hydrogenation Using Composite Iron Carbide Nanoparticles of Exceptionally High Heating Power.

The use of magnetic nanoparticles to convert electromagnetic energy into heat is known to be a key strategy for numerous biomedical applications but is also an approach of growing interest in the field of catalysis. The heating efficiency of magnetic nanoparticles is limited by the poor magnetic properties of most of them. Here we show that the new generation of iron carbide nanoparticles of controlled size and with over 80 % crystalline Fe2.2 C leads to exceptional heating properties, which are much better than the heating properties of currently available nanoparticles. Associated to catalytic metals (Ni, Ru), iron carbide nanoparticles submitted to magnetic excitation very efficiently catalyze CO2 hydrogenation in a dedicated continuous-flow reactor. Hence, we demonstrate that the concept of magnetically induced heterogeneous catalysis can be successfully applied to methanation of CO2 and represents an approach of strategic interest in the context of intermittent energy storage and CO2 recovery.