Active Catalyst Research Articles

Addition of Imidazolium-Based Ionic Liquid to Improve Methanol Production in Polyamine-Assisted CO2 Capture and Conversion Systems Using Pincer Catalysts.

Ionic liquids have been studied as CO2 capture agents. However, they are rarely used in combined CO2 capture and conversion processes. Utilizing imidazolium-based ionic liquids, the conversion of CO2 to methanol was greatly improved in polyamine assisted systems catalyzed by homogeneous pincer catalysts with Ru and Mn metal centers. Among the ionic liquids tested, [BMIM]OAc was found to perform the best under the given reaction conditions. Among the polyamine tested, pentaethylenehexamine (PEHA) led to the highest conversion rates. Ru-Macho and Ru-Macho-BH were the most active catalysts. Direct air capture utilizing PEHA as the capture material was also demonstrated and produced an 86 % conversion of the captured CO2 to methanol in the presence of [BMIM]OAc.

Catalytic activity of Ni–Cr–Fe–Mo porous materials for hydrogen evolution reaction in alkaline media

The hydrogen evolution reaction (HER) based on water electrolysis represents an ideal approach for hydrogen production. The advancement of highly active non-precious metal catalysts holds paramount importance. This research employed powder metallurgy sintering to prepare Ni–Cr–Fe and Ni–Cr–Fe–Mo porous materials. It investigated the impact of Mo doping and sintering temperature on the catalytic activity and microstructural influence of hydrogen evolution materials. Furthermore, the materials' electrochemical performance and long-term stability in 6 mol/L KOH were examined. In complicated systems, the current work provides a feasible method for producing hydrogen from Ni–Cr–Fe–Mo porous materials in a strong alkali environment. The results exhibited that when Mo content is 5% and the sintering temperature is 800 °C, the porosity of Ni–Cr–Fe–Mo porous materials is up to 39.9% and the catalytic activity is up to 97%. At the same time, the current density decays to 7.1% after 1000 cycles of electrolysis and shows good HER stability after 48 h. The enhanced catalytic activity for hydrogen evolution emanated from the positive synergy among the transition metal elements.

A Phosphine-Oxide Cobalt(II) Complex and Its Catalytic Activity Studies toward Alcohol Dehydrogenation Triggered Direct Synthesis of Imines and Quinolines.

Herein, a new pincer-like amino phosphine donor ligand, H2L1, and its phosphine-oxide analog, H2L2, were synthesized. Subsequently, cobalt(II) complexes 1 and 2 were synthesized by the reaction of anhydrous Co(II)Cl2 with ligands H2L1 and H2L2, respectively. The ligands and complexes were fully characterized by various physicochemical and spectroscopic characterization techniques. Finally, the identity of the complexes 1 and 2 was confirmed by single crystal X-ray structure determination. The phosphine ligand containing complex 1 was converted to the phosphine oxide ligand containing complex 2 in air in acetonitrile solution. Both complexes 1 and 2 were investigated as precatalysts for alcohol dehydrogenation-triggered synthesis of imines in air. The phosphine-oxide complex 2 was more efficient than the phosphine complex 1. A wide array of alcohols and amines were successfully reacted in a mild condition to result in imines in good to excellent yields. Precatalyst 2 was also highly efficient for the synthesis of varieties of quinolines in air. As H2L2 in 2 has side arms that can be deprotonated, we investigated complex 2 for its base (KOtBu) promoted deprotonation events by various spectroscopic studies and DFT calculations. These studies have shown that mono deprotonation of the amine side arm attached to the pyridine is quite feasible, and deprotonation of complex 2 leads to a dearomatized pyridyl ring containing complex 2a. The mechanistic investigations of the catalytic reaction, by a combination of experimental and computational studies, have suggested that the dearomatized complex, 2a acted as an active catalyst. The reaction proceeded through the hydride transfer pathway. The activation barrier of this step was calculated to be 26.5 kcal/mol, which is quite consistent with the experimental reaction temperature under aerobic conditions. Although various pincer-like complexes are explored for such reactions, phosphine oxide ligand-containing complexes are still unexplored.

Unlocking Photocatalytic Activity of Acridinium Salts by Anion-Binding Co-Catalysis.

The in situ generation of active photoredox organic catalysts upon anion-binding co-catalysis by making use of the ionic nature of common photosensitizers is reported. Hence, the merge of anion-binding and photocatalysis permitted the modulation of the photocatalytic activity of simple acridinium halide salts, building an effective anion-binding - photoredox ion pair complex able to promote a variety of visible light driven transformations, such as anti-Markovnikov addition to olefins, Diels-Alder and the desilylative C-C bond formatting reactions. Anion-binding studies, together with steady-state and time-resolved spectroscopy analysis, supported the postulated ion pair formation between the thiourea hydrogen-bond donor organocatalyst and the acridinium salt, which proved essential for unlocking the photocatalytic activity of the photosensitizer.

Multiple phase transformation of ZIF-L to LDH and Ag nanoparticles decorated on CoNi layered double hydroxides for high-performance supercapacitor and highly efficient hydrogen evolution reaction

ZIF-L-derived binary layered double hydroxide (LDH) established active catalysts have been shown to have potential as electrode materials in the development of high-performance supercapacitors (SCs) and hydrogen evaluation reactions (HER). This study uses conductive nano-silver (Ag) particles in hierarchically integrated CoNi-LDH nanosheets (NSs), which are described. The developed Ag@CoNi-LDH NSs electrode has a very high specific capacitance of 2878 F g−1 at 0.5 A g−1 and an impressive rate capability. This is due to consistent morphology, plentiful electroactive sites, homogeneous particle size, and decreased electronic/ionic impedance. The fabrication of solid-state hybrid supercapacitors (HSCs) using Ag@CoNi-LDH NSs as the positive electrode and activated carbon (AC) as the negative electrode in PVA/KOH polymer gel electrolytes has been described. The prepared supercapacitors achieve a maximum energy density of 105 Wh kg−1 at power densities of 1183 Wh kg−1, coupled with excellent initial capacitance retentions of 97 % after 20,000 cycles. Ag@CoNi-LDH NSs demonstrate effective electrocatalytic activity towards HER with an ultra-low overpotential of 26 mV at 10 mA cm−2 and the associated Tafel value of 35 mV dec−1 using 0.5 M acidic electrolyte. It is possible to attribute the extraordinary electrochemical performance to the thoughtful mixture of two electroactive materials in the future.

Thermochemical Activation of Wood with NaOH, KOH and H3PO4 for the Synthesis of Nitrogen-Doped Nanoporous Carbon for Oxygen Reduction Reaction

Carbonization of biomass residues followed by activation has great potential to become a safe process for the production of various carbon materials for various applications. Demand for commercial use of biomass-based carbon materials is growing rapidly in advanced technologies, including in the energy sector, as catalysts, batteries and capacitor electrodes. In this study, carbon materials were synthesized from hardwood using two carbonization methods, followed by activation with H3PO4, KOH and NaOH and doping with nitrogen. Their chemical composition, porous structure, thermal stability and structural order of samples were studied. It was shown that, despite the differences, the synthesized carbon materials are active catalysts for oxygen reduction reactions. Among the investigated carbon materials, NaOH-activated samples exhibited the lowest Tafel slope values, of −90.6 and −88.0 mV dec–1, which are very close to the values of commercial Pt/C at −86.6 mV dec–1.

Influence of the alcohol and water grades on surfactant-free colloidal syntheses of gold nanoparticles in alkaline water-alcohol mixtures

AbstractTo make the most of the unique properties of nanomaterials, and to bridge the gap between fundamental and applied research, controlled, green, cheap and energy efficient syntheses of nanoparticles are required. In this respect, room and low temperature surfactant-free colloidal syntheses of nanoparticles obtained in low viscosity and low boiling point solvents, without additives or nature-derived extracts, are promising to develop more active (electro)catalysts. Recently, a room temperature synthesis of surfactant-free gold nanoparticles has been documented (Chem. Mater. 2023, 35, 5, 2173) that requires only water, a base such as NaOH, an alcohol and HAuCl4. Unfortunately, the syntheses of nanomaterials are often sensitive to multiple parameters and it is well acknowledged that reproducibility is a general challenge in the chemical sciences, where the synthesis of nanomaterials is no exception. Here, we investigate the effect of the water conductivity and solvent grade on the surfactant-free low temperature (ca. 30 °C) synthesis of colloidal gold nanoparticles obtained in alkaline mixtures of ethanol and water. The synthesis can be performed with relatively low-grade ethanol but requires high purity water. The importance of water with low conductivity is also stressed for syntheses where ethylene glycol and glycerol are used as source of reducing agents. The results of this study over 100 samples pave the way to greener, more controlled and scalable syntheses of surfactant-free gold nanomaterials.

Magnetic Aerogels for Room-Temperature Catalytic Production of Bis(indolyl)methane Derivatives

The potential of aerogels as catalysts for the synthesis of a relevant class of bis-heterocyclic compounds such as bis(indolyl)methanes was investigated. In particular, the studied catalyst was a nanocomposite aerogel based on nanocrystalline nickel ferrite (NiFe2O4) dispersed on amorphous porous silica aerogel obtained by two-step sol–gel synthesis followed by gel drying under supercritical conditions and calcination treatments. It was found that the NiFe2O4/SiO2 aerogel is an active catalyst for the selected reaction, enabling high conversions at room temperature, and it proved to be active for three repeated runs. The catalytic activity can be ascribed to both the textural and acidic features of the silica matrix and of the nanocrystalline ferrite. In addition, ferrite nanocrystals provide functionality for magnetic recovery of the catalyst from the crude mixture, enabling time-effective separation from the reaction environment. Evidence of the retention of species involved in the reaction into the catalyst is also pointed out, likely due to the porosity of the aerogel together with the affinity of some species towards the silica matrix. Our work contributes to the study of aerogels as catalysts for organic reactions by demonstrating their potential as well as limitations for the room-temperature synthesis of bis(indolyl)methanes.

PIP2 Is An Electrostatic Catalyst for Vesicle Fusion by Lowering the Hydration Energy: Arresting Vesicle Fusion by Masking PIP2.

Lipids are key factors in regulating membrane fusion. Lipids are not only structural components to form membranes but also active catalysts for vesicle fusion and neurotransmitter release, which are driven by soluble N-ethylmaleimide-sensitive factor attachment protein receptor (SNARE) proteins. SNARE proteins seem to be partially assembled before fusion, but the mechanisms that arrest vesicle fusion before Ca2+ influx are still not clear. Here, we show that phosphatidylinositol 4,5-bisphosphate (PIP2) electrostatically triggers vesicle fusion as an electrostatic catalyst by lowering the hydration energy and that a myristoylated alanine-rich C-kinase substrate (MARCKS), a PIP2-binding protein, arrests vesicle fusion in a vesicle docking state where the SNARE complex is partially assembled. Vesicle-mimicking liposomes fail to reproduce vesicle fusion arrest by masking PIP2, indicating that native vesicles are essential for the reconstitution of physiological vesicle fusion. PIP2 attracts cations to repel water molecules from membranes, thus lowering the hydration energy barrier.

Double core–shell hollow nanocage CuO@Co3O4 for the selective hydrogenolysis of C–O bonds of lignin without external hydrogen

The design of a highly active Cu-Co catalyst for catalytic transfer hydrogenolysis of lignin without the use of external hydrogen remains highly challenging. In this work, Cu2O was initially encapsulated in ZIF-67, and subsequently Cu2O@ZIF-67 was utilized as a precursor and sacrificial template to prepare the unique double core–shell hollow nanocage CuO@Co3O4. Co and Cu, serving as Lewis acid sites and dehydrogenation sites for the hydrogen-donor solvent isopropanol, respectively, exhibited synergistic enhancement, further increasing the catalytic activity. Under the optimal conditions of 220 °C, 1 MPa N2, and 4 h, the catalyst achieved 100 % conversion of 2-phenoxy-1-phenylethanol and 100 % yield towards cyclohexanol and ethylbenzene. Furthermore, the catalyst remained stable and reusable after 5 cycles, providing a practicable guidance for the value-added conversion of lignin.

Rational Design of Ultrafine Pt Nanoparticles with Strong Metal‐Support Interaction for Efficient Hydrogen Evolution

AbstractHydrogen evolution reaction (HER) plays an indispensable role in hydrogen economy. However, the development of highly active and durable Pt catalysts remains a great challenge. A homogenously‐dispersed, ultrafine and chemically anchored Pt‐based catalyst is successfully synthesized with the regulation of ‐SH groups tethered to SBA‐15 template. The ‐SH not only regulates the particle size of Pt, but also modifies the chemical environment of the carbon support by converting itself into heteroatom—S. The obtained catalyst (Pt/OMCSH) exhibits superior HER catalytic activity (15.4 mV at 10 mA cm−2; 28.4 mV dec−1; 1.0 M KOH) and stability to benchmark samples and most of the previously reported Pt‐based electrocatalysts. First‐principles calculations reveal that the presence of S in the carbon support regulates the electronic structure of Pt and strengthens the metal‐support interaction, thus boosting the reaction kinetics and enhancing the stability of Pt/OMCSH catalyst for HER.

Effect of Ag Addition to Au Catalysts for the Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid

AbstractThe addition of Ag to Au nanocatalysts is known to improve several catalytic reduction and oxidation reactions. Until now, bimetallic AuAg catalysts have not been studied in detail in liquid phase oxidation reactions. We investigated the activity, selectivity, and stability of silica supported Au, Ag and AuAg catalysts in the oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA), an important reaction to produce bio‐based polymers. We demonstrate that addition of an optimum amount of inactive Ag to the active Au catalyst substantially increases the overall selectivity and yield of the desired FDCA. Interestingly, Ag addition decreased the conversion rate of the reactant HMF to the intermediate HMFCA, but improved (up to 10–20 % Ag addition) much the conversion of the intermediate product to the desired final product. This is probably due to tuning the electronic properties of the nanoparticles to achieve an optimum adsorption strength of the intermediate on the surface of AuAg catalysts. Moreover, particle growth was suppressed by the bimetallic AuAg catalyst, ultimately leading to superior stability compared to its monometallic counterparts.

Theoretical study of transition metal-doped β12 borophene as a new single-atom catalyst for carbon dioxide electroreduction.

The electrocatalytic carbon dioxide reduction reaction (CO2RR) presents a viable and cost-effective approach for the elimination of CO2 by transforming it into valuable products. Nevertheless, this process is impeded by the absence of exceptionally active and stable catalysts. Herein, a new type of electrocatalyst of transition metal (TM)-doped β12-borophene (TM@β12-BM) is investigated via density functional theory (DFT) calculations. Through comprehensive screening, two promising single-atom catalysts (SACs), Sc@β12-BM and Y@β12-BM, are successfully identified, exhibiting high stability, catalytic activity and selectivity for the CO2RR. The C1 products methane (CH4) and methanol (CH3OH) are synthesized with limiting potentials (UL) of -0.78 V and -0.56 V on Sc@β12-BM and Y@β12-BM, respectively. Meanwhile, CO2 is more favourable for reduction into the C2 product ethanol (CH3CH2OH) compared to ethylene (C2H4) via C-C coupling on these two SACs. More importantly, the dynamic barriers of the key C-C coupling step are 0.53 eV and 0.73 eV for the "slow-growth" sampling approach in the explicit water molecule model. Furthermore, Sc@β12-BM and Y@β12-BM exhibit higher selectivity for producing C1 compounds (CH4 and CH3OH) than C2 (CH3CH2OH) in the CO2RR. Compared with Sc@β12-BM, Y@β12-BM demonstrates superior inhibition of the competitive hydrogen evolution reaction (HER) in the liquid phase. These results not only demonstrate the great potential of SACs for direct reduction of CO2 to C1 and C2, but also help in rationally designing high-performance SACs.

Mechanistic Insights into Electrocatalytic Hydrogen Evolution by an Exceptionally Stable Cobalt Complex.

Co(aPPy) is one of the most stable and active molecular first-row transition-metal catalysts for proton reduction reported to date. Understanding the origin of its high performance via mechanistic studies could aid in developing even better catalysts. In this work, the catalytic mechanism of Co(aPPy) was electrochemically probed, in both organic solvents and water. We found that different mechanisms can occur depending on the solvent and the acidity of the medium. In organic solvent with a strong acid as the proton source, catalysis initiates directly after a single-electron reduction of CoII to CoI, whereas in the presence of a weaker acid, the cobalt center needs to be reduced twice before catalysis occurs. In the aqueous phase, we found drastically different electrochemical behavior, where the Co(aPPy) complex was found to be a precatalyst to a different electrocatalytic species. We propose that in this active catalyst, the pyridine ring has dissociated and acts as a proton relay at pH ≤ 5, which opens up a fast protonation pathway of the CoI intermediate and results in a high catalytic activity. Furthermore, we determined with constant potential bulk electrolysis that the catalyst is most stable at pH 3. The catalyst thus functions optimally at low pH in an aqueous environment, where the pyridine acts as a proton shuttle and where the high acidity also prevents catalyst deactivation.

CO2‐Steam Bi‐Reforming of Methane Over La1−xSrxNi0.8Zr0.2O3 Perovskite Catalysts to Generate Hydrogen Rich Syngas

AbstractThe present study proposes La and Sr‐containing La1−xSrxNi0.8Zr0.2O3 (x=0.1, 0.2, 0.4, 0.6, 0.8) perovskites as potential catalysts for bi‐reforming of methane (BRM) with CO2 and steam to produce hydrogen rich syngas. The catalysts were prepared by sol‐gel method and characterized using various techniques such as XRD, H2‐TPR, BET, CO2‐TPD and CHNS analysis. The characterization studies revealed that metal‐support interaction increased with the increase in the composition of Sr and the reduction behavior of Ni found to vary with the addition of Sr. The total energy calculations reveal that the addition of Sr to the LNZ system shirnks the volume due to low atomic and high ionic radii of Sr over La, which increases the total energy of system driving towards instability with increasing doping concentration of Sr. CO2‐TPD results suggest that a small amount of Sr can change the basicity of the support. The BRM activity results revealed that La0.8Sr0.2Ni0.8Zr0.2O3 perovskite is the most promising and active catalyst. The proposed catalysts are found to be advantageous w.r.t less carbon deposition due to the increased dispersion, small crystalline size, and required basicity of the support. The disclosed catalyst has shown excellent stability for a studied period of 100 h.

Evaluation of indole-based organometallics as transfer hydrogenation catalysts with anticancer activity

Half-sandwich complexes containing transition metals offer a wide range of applications owing to their interactions with a variety of targets/molecules that are not accessible for some organic scaffolds. The use of such complexes is therefore a way to provide new mechanisms of drug action. Here, we report a series of neutral metal complexes of the type [(arene)M(O-cyclohexyl-1H-indole-2-carbothiolate)Cl] that have the ability to reduce the coenzyme NAD+ at physiological conditions in the presence of sodium formate as an hydride donor. The influence of the metal ion (Ru, Os, Rh, Ir) is studied to establish some structure-activity relationships. The [(η6-p-cym)Ru(O-cyclohexyl-1H-indole-2-carbothioate)Cl] is the most active catalyst of this family of complexes with a turnover frequency (TOF) of 14.79 h-1 for the transfer hydrogenation reaction of NAD+ to give 1,4-NADH in the presence of formate. Further in vitro studies were carried out to determine a relationship between catalytic activity and potency as an anticancer drug, with the rhodium complex promisingly showing 7x more selectivity towards cancer cells (A2780) than normal cells (PNT2). Preliminary in vivo studies demonstrated the importance of co-treatment with formate to enhance activity. This work gives insights into the mechanism of action of this family of indole-based organometallic complexes.

CO to Isonitrile Substitution in Iron Cyclopentadienone Complexes: A Class of Active Iron Catalysts for Borrowing Hydrogen Strategies

CO to Isonitrile Substitution in Iron Cyclopentadienone Complexes: A Class of Active Iron Catalysts for Borrowing Hydrogen Strategies

Waste Biomass-Derived Activated Carbon-Supported 0D, 1D, 2D, and 3D Nanostructures of Copper Oxide for Hydrogenation Reaction: A Study on the Role of Structural Properties.

Intensive attention is given to the morphology-controlled synthesis of inorganic nanomaterials because of their intrinsic shape-dependent properties. In this article, different dimensions (D) of copper oxide (CuO) nanoparticles (such as 0D-sphere, 1D-rod, 1D-belt, 2D-rolling pin sheets, 3D-octahedron, and 3D-throne) are prepared. The catalytic efficacy of these differently shaped CuO catalysts is compared for hydrogenation reactions under reducing agent-free conditions. The order of catalytic activity of the CuO catalyst is found to be belt > octahedron > rolling pin > rod > sphere > throne. The best catalyst among the different shaped CuO catalysts, namely belt shape, is supported on the functionalized groundnut shells activated carbon sheets (FGNC). Interestingly, 25 wt % CuO/FGNC catalysts exhibit the highest catalytic activity for the reduction of nitro compounds. Importantly, the highly active FGNC-supported catalyst is reused for up to 10 cycles without any noticeable loss in the catalytic activity.

Elucidating the Mechanism of Tetrahydrofuran-Diol Formation through Os(VI)-Catalyzed Oxidative Cyclization of 5,6-Dihydroxyalkenes Ligated by Citric Acid.

A computational study is reported here on the mechanism of tetrahydrofuran (THF)-diol formation from the Os(VI)-catalyzed oxidative cyclization of 5,6-dihydroxyalkene ligated with citric acid and in the presence of Bro̷nsted acid. Initiated by Os(VI) dioxo citrate formation, coordination of co-oxidant pyridine-N-oxide (PNO) and protonation of its oxo group generate the active catalyst. The catalytic cycle commences through successive steps, including dihydroxyalkene addition to the active catalyst in a concerted mechanism to form hexacoordinated alkoxy-protonated PNO-complexed Os(VI) bisglycolate as a turnover-limiting step (TLS), cyclization to Os(IV) THF-diolate, reoxidation to Os(VI) THF-diolate, and hydrolysis via a dissociative mechanism to furnish the THF-diol and regenerate the active species, sustaining the catalytic cycle through an Os(VI)/Os(IV) cycle. Despite the overall exergonic nature of catalytic cycle (ΔGrcycle = -45.0 kcal/mol), the TLS is accelerated by the formation of an open-valence 16-electron Os(VI) intermediate but decelerated by the undesired formation of a saturated/hexacoordinate 18-electron Os(VI) intermediate. Bro̷nsted acid plays crucial roles in the formation of Os(VI) citrate and the active catalyst, impediment of the second cycle, and the cyclization step. Additionally, besides its role as a co-oxidant, and in the presence of acid, PNO is found to assist the insertion of dihydroxyalkene and, importantly, in releasing the THF-diol to regenerate the active intermediate.

An active, stable cubic molybdenum carbide catalyst for the high-temperature reverse water-gas shift reaction.

Although technologically promising, the reduction of carbon dioxide (CO2) to produce carbon monoxide (CO) remains economically challenging owing to the lack of an inexpensive, active, highly selective, and stable catalyst. We show that nanocrystalline cubic molybdenum carbide (α-Mo2C), prepared through a facile and scalable route, offers 100% selectivity for CO2 reduction to CO while maintaining its initial equilibrium conversion at high space velocity after more than 500 hours of exposure to harsh reaction conditions at 600°C. The combination of operando and postreaction characterization of the catalyst revealed that its high activity, selectivity, and stability are attributable to crystallographic phase purity, weak CO-Mo2C interactions, and interstitial oxygen atoms, respectively. Mechanistic studies and density functional theory (DFT) calculations provided evidence that the reaction proceeds through an H2-aided redox mechanism.