Catalytic Activation Research Articles

Ultra-high dispersion of Ni-based OER catalysts on graphene 3D networks enhances the in situ Fe3+ catalytic activation

Ultradispersed and nanosized Ni-based particles supported on 3D graphene networks by a freeze-casting method exhibit good catalytic properties towards the OER and outstanding Fe-ion activation from the impurities present in the alkaline electrolyte.

H/D exchange studies of methane activation mechanisms in heterogeneous catalysis

The development of technologies for the efficient conversion of methane and other light hydrocarbons is becoming vital to the chemical industry. The main technologies for methane conversion are based on solid and liquid catalysts such as metals, oxides and oxide-supported metals. Methane is a highly stable molecule, and the analysis of the catalytic activity of materials with respect to the C-H bond cleavage in methane is of paramount importance for the development of novel methane conversion catalysts. One of the most promising methods for studying methane activation over a catalyst is H/D isotope exchange between the gas and condensed phases. The method provides reliable in situ information on the cleavage of chemical bonds in molecules and allows researchers to elucidate the elementary steps of catalytic methane activation and the stable intermediates involved in the activation process. This paper focuses on the critical analysis of H/D isotope exchange studies of the methane activation mechanism over various metals, oxides, composites, and other catalysts, from the earlier studies to the recent advances in the field. The existing theoretical and experimental approaches to study the H/D exchange between methane and a catalyst are discussed in the paper. A critical analysis of the structure-composition-catalytic activity relationships of the catalysts with respect to methane activation is provided.

Co-assembly-mediated biosupramolecular catalysis: thermodynamic insights into nucleobase specific (oligo)nucleotide attachment and cleavage.

Gaining control over the stability and cleavage of phosphoester and phosphodiester remains a matter of interest for their application in biotechnology to oligonucleotide-based therapeutics. Herein, we report an efficient unactivated phosphoester hydrolysis (stable mono/di/tri/cyclic nucleotide to nucleoside conversion) via a biosupramolecular system comprising of a non-covalent complex of enzyme, alkaline phosphatase (ALP), and Zn(II)-metallosurfactant. We also demonstrate the nucleobase selective activation or inhibition of ALP-mediated oligonucleotide digestion process using that complex. The higher binding affinity of Zn(II)-containing headgroup with phosphate-containing substrate enhanced the effective substrate concentration surrounding the enzyme, which, in turn, results in a drastic decrease in the Michaelis constant (KM), along with an increase in the turnover (kcat). The catalytic activation or inhibition of nucleobase-specific oligonucleotide digestion depends on the hydration, localization of the substrates, and viscosity of the resultant co-assembly upon substrate binding with the enzyme-metallosurfactant complex. Additionally, through isothermal titration calorimetry experiment, we demonstrate enthalpy-entropy change during both the supramolecular binding of (oligo)nucleotides and simultaneous activation/inhibition in catalytic cleavage. Overall, it showed the possible modularity of Zn(II)-mediated biosupramolecular interaction, describing intrinsic thermodynamic aspects in developing complex biocatalytic circuits with nucleobase-specific oligonucleotides inputs, which are relevant in designing nucleic acid-based cargo for drug delivery and bioimaging.

Catalytic activation of remote alkenes through silyl-rhodium(III) complexes.

The tandem isomerization-hydrosilylation reaction is a highly valuable process able to transform mixtures of internal olefins into linear silanes. Unsaturated and cationic hydrido-silyl-Rh(III) complexes have proven to be effective catalysts for this reaction. Herein, three silicon-based bidentate ligands, 8-(dimethylsilyl)quinoline (L1), 8-(dimethylsilyl)-2-methylquinoline (L2) and 4-(dimethylsilyl)-9-phenylacridine (L3), have been used to synthesize three neutral [RhCl(H)(L)PPh3] (1-L1, 1-L2 and 1-L3) and three cationic [Rh(H)(L)(PPh3)2][BArF4] (2-L1, 2-L2 and 2-L3) Rh(III) complexes. Among the neutral compounds, 1-L2 could be characterized in the solid state by X-ray diffraction showing a distorted trigonal bipyramidal structure. Neutral complexes (1-L1, 1-L2 and 1-L3) failed to catalyze the hydrosilylation of olefins. On the other hand, the cationic compound 2-L2 was also characterized by X-ray diffraction showing a square pyramidal structure. The unsaturated and cationic Rh(III) complexes 2-L1, 2-L2 and 2-L3 showed significant catalytic activity in the hydrosilylation of remote alkenes, with the most sterically hindered (2-L2) being the most active one.

Anomalous π-backbonding in complexes between B(SiR3)3 and N2: catalytic activation and breaking of scaling relations.

Chemical transformations of molecular nitrogen (N2), including the nitrogen reduction reaction (NRR), are difficult to catalyze because of the weak Lewis basicity of N2. In this study, it is shown that Lewis acids of the types B(SiR3)3 and B(GeR3)3 bind N2 and CO with anomalously short and strong B-N or B-C bonds. B(SiH3)3·N2 has a B-N bond length of 1.48 Å and a complexation enthalpy of -15.9 kcal mol-1 at the M06-2X/jun-cc-pVTZ level. The selective binding enhancement of N2 and CO is due to π-backbonding from Lewis acid to Lewis base, as demonstrated by orbital analysis and density difference plots. The π-backbonding is found to be a consequence of constructive orbital interactions between the diffuse and highly polarizable B-Si and B-Ge bond regions and the π and π* orbitals of N2. This interaction is strengthened by electron donating substituents on Si or Ge. The π-backbonding interaction is predicted to activate N2 for chemical transformation and reduction, as it decreases the electron density and increases the length of the N-N bond. The binding of N2 and CO by the B(SiR3)3 and B(GeR3)3 types of Lewis acids also has a strong σ-bonding contribution. The relatively high σ-bond strength is connected to the highly positive surface electrostatic potential [VS(r)] above the B atom in the tetragonal binding conformation, but the σ-bonding also has a significant coordinate covalent (dative) contribution. Electron withdrawing substituents increase the potential and the σ-bond strength, but favor the binding of regular Lewis acids, such as NH3 and F-, more strongly than binding of N2 and CO. Molecules of the types B(SiR3)3 and B(GeR3)3 are chemically labile and difficult to synthesize. Heterogenous catalysts with the wanted B(Si-)3 or B(Ge-)3 bonding motif may be prepared by boron doping of nanostructured silicon or germanium compounds. B-doped and hydrogenated silicene is found to have promising properties as catalyst for the electrochemical NRR.

Processive binding mechanism of Cel9G from Clostridium cellulovorans: molecular dynamics and free energy landscape investigations.

The degradation of recalcitrant polysaccharides such as cellulose and chitin requires the synergistic functionality of processive glycosidase (GH) cocktails. Understanding the fundamental phenomenon of processivity is of biological and economic importance for the conversion of biomass into biofuel. In this work, cellulase family 9 from Clostridium cellulovorans (Cel9G), which is a processive endoglucanase, was used to elucidate the processive binding mechanism with respect to polysaccharides, since it exhibits a multimodular crystallographic structure. Metadynamics and molecular dynamics simulations were performed to explore the dynamics of cellulose chain binding to Cel9G via processive motion. The processive movement of the cellulose chain towards the catalytic domain may exhibit several local minima, which are related to strong CH/π interactions between the sugar rings and the aromatic residues distributed at the active site. For the binding of the G6 and G12 molecules, the energy barriers were determined to be 4.8 and 7.4 kcal mol-1, respectively. Based on the site-directed mutagenesis simulations of Y520A, it was found that the existence of Y520 is critical for processive binding. It is likely that Y520 and H125/Y416 form two anchor points to facilitate processive binding to polysaccharides. More importantly, the straight-line morphology of the substrate could be observed after the formation of the so-called slide mode, which is different from the V-shaped Michaelis complex structure revealed by quantum mechanics/molecular mechanics simulations. This indicates that an additional step, namely, catalytic activation, probably exists between processive binding and the hydrolysis reaction. Finally, a four-step catalytic cycle was proposed for Cel9G. Our work provides novel molecular-level insights into the structure-function relationship for the processive enzyme Cel9G and should aid the development of improved GH cocktails for the efficient cleavage of glycosidic linkages.

Iron(II)-α-keto acid complexes of tridentate ligands on gold nanoparticles: the effect of ligand geometry and immobilization on their dioxygen-dependent reactivity.

Two mononuclear nonheme iron(II)-benzoylformate (BF) complexes [(6Me2-Me-BPA)Fe(BF)](ClO4) (1a) and [(6Me3-TPMM)Fe(BF)](ClO4) (1b) of tridentate nitrogen donor ligands, bis((6-methylpyridin-2-yl)methyl)(N-methyl)amine (6Me2-Me-BPA) and tris(2-(6-methyl)pyridyl)methoxymethane (6Me3-TPMM), were isolated and characterized. The structural characterization of iron(II)-chloro complexes indicates that the ligand 6Me2-Me-BPA binds to the iron(II) centre in a meridional fashion, whereas 6Me3-TPMM behaves as a facial ligand. Both the ligands were functionalized with terminal thiol for immobilization on gold nanoparticles (AuNPs), and the corresponding iron(II) complexes [(6Me2-BPASH)Fe(BF)(ClO4)]@C8Au (2a) and [(6Me3-TPMSH)Fe(BF)(ClO4)]@C8Au (2b) were prepared to probe the effect of immobilization on their ability to perform bioinspired oxidation reactions. All the complexes react with dioxygen to display the oxidative decarboxylation of the coordinated benzoylformate, but the complexes supported by 6Me3-TPMM and its thiol-appended ligand display faster reactivity compared to their analogues with the 6Me2-Me-BPA-derived ligands. In each case, an electrophilic iron-oxygen oxidant was intercepted as the active oxidant generated from dioxygen. The immobilized complexes (2a and 2b) display enhanced O2-dependent reactivity in oxygen-atom transfer reactions (OAT) and hydrogen-atom transfer (HAT) reactions compared to their homogeneous congeners (1a and 1b). Furthermore, the immobilized complex 2b displays catalytic OAT reactions. This study supports that the ligand geometry and immobilization on AuNPs influence the dioxygen-dependent reactivity of the complexes.

Mechanochemical solid state single electron transfer from reduced organic hydrocarbon for catalytic aryl-halide bond activation.

Solid-state radical generation is an attractive but underutilized methodology in the catalytic strong bond activation process, such as the aryl-halide bond. Traditionally, such a process of strong bond activation relied upon the use of transition metal complexes or strongly reducing photocatalysts in organic solvents. The generation of the aryl radical from aryl halides in the absence of transition-metal or external stimuli, such as light or cathodic current, remains an elusive process. In this study, we describe a reduced organic hydrocarbon, which can act as a super reductant in the solid state to activate strong bonds by solid-state single electron transfer (SSSET) under the influence of mechanical energy leading to a catalytic strategy based on the mechano-SSSET or mechanoredox process. Here, we investigate the solid-state synthesis of the super electron donor phenalenyl anion in a ball mill and its application as an active catalyst in strong bond (aryl halide) activation. Aryl radicals generated from aryl halides by employing this strategy are competent for various carbon-carbon bond-forming reactions under solvent-free and transition metal-free conditions. We illustrate this approach for partially soluble or insoluble polyaromatic arenes in accomplishing solid-solid C-C cross-coupling catalysis, which is otherwise difficult to achieve by traditional methods using solvents.

Electrophilic activation of molecular bromine mediated by I(III).

In pursuit of a genuine bromo-λ3-iodane, it has been found that the combination of Br2 and electron deficient λ3-iodanes can result in the delivery of both bromine atoms from Br2 to a range of aryl substrates, some highly deactivated. These brominations occur rapidly in common chlorinated solvents at room temperature and can be achieved with the catalytic activation of commercially available PhI(OAc)2 and PhI(OTFA)2. para-NO2 substituted derivatives are employed to direct bromination towards more deactivated substrates. The mechanism of Br2 activation is discussed with insights being made, however it remains unclear.

Spiers Memorial Lecture: Catalytic activation of molecular nitrogen for green ammonia synthesis: introduction and current status.

The efficient synthesis of ammonia using carbon-footprint-free hydrogen under mild conditions is a grand challenge in chemistry today. To achieve this objective, novel concepts are needed for the activation process and catalyst. This article briefly reviews catalytic activation of N2 for ammonia synthesis under mild conditions. The features of the various activation methods reported so far are summarized, looking chronologically back at progress in heterogeneous catalysts since the use of iron oxide for the Haber-Bosch process, and finally the technical challenges to be overcome are described. Establishing low work functions for the support materials of the metal catalysts is one key to reducing the activation barrier to dissociate N2. Surfaces of electride materials that preserve the character of the bulk are shown to be useful for this purpose. The requirements of desired catalysts are high efficiency at low temperatures, Ru-free compositions, and chemical robustness in the ambient atmosphere.

Catalytic activation of peroxymonosulfate by Mn/N co-doped porous carbon for effective phenol degradation: crucial role of non-radical pathways

A manganese–nitrogen co-doped porous carbon with high nitrogen content was prepared to improve the contribution rate of non-radical pathways to the degradation process of organic pollutants.

Catalysis enabled synthesis, structures, and reactivities of fluorinated S8-corona[n]arenes (n = 8-12).

Previously inaccessible large S8-corona[n]arene macrocycles (n = 8-12) with alternating aryl and 1,4-C6F4 subunits are easily prepared on up to gram scales, without the need for chromatography (up to 45% yield, 10 different examples) through new high acceleration SNAr substitution protocols (catalytic NR4F in pyridine, R = H, Me, Bu). Macrocycle size and functionality are tunable by precursor and catalyst selection. Equivalent simple NR4F catalysis allows facile late-stage SNAr difunctionalisation of the ring C6F4 units with thiols (8 derivatives, typically 95+% yields) providing two-step access to highly functionalised fluoromacrocycle libraries. Macrocycle host binding supports fluoroaryl catalytic activation through contact ion pair binding of NR4F and solvent inclusion. In the solid-state, solvent inclusion also intimately controls macrocycle conformation and fluorine-fluorine interactions leading to spontaneous self-assembly into infinite columns with honeycomb-like lattices.

Ppb-Level Detection Triethylamine Gas Sensor Based on Ag-Doped Nanosheets-Assembled Octahedron Zn2SnO4

The current semiconductor sensors cannot detect the ultra-low concentration of triethylamine (TEA). Therefore, this paper uses the catalytic activation effect of precious metal silver and combined with the unique physical and chemical properties of ternary metal oxides to design the Ag-doped Zn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> SnO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> gas sensor to detect the ultra-low concentration of TEA. In this work, spinel-type metal oxides Zn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> SnO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> was prepared by one-step hydrothermal method and its functional modification by means of precious metal doping. The countenance and elemental content of the synthesized products were dissected through diverse means. Combined with the characterization data, it is shown that Zn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> SnO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> samples all present a fixed octahedral shape and the surface is assembled by a large number of nanoplates. The gas sensing test results show that the gas sensor based on 3at% (atom percent) Ag doped Zn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> SnO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> has the best gas sensing performance for TEA. Its response to 100 ppm TEA at 250°C is 273.33. At the same time, the minimum detectable concentration level is 100 ppb. In addition, the material also demonstrates fast response time, good stability and high selectivity. The excellent gas sensing performance is mainly attributed to the synergistic effect of chemical sensitization and electron sensitization of precious metal silver.

Catalytic Activation of Hydrogen Peroxide Using Highly Porous Hydrothermally Modified Manganese Catalysts for Removal of Azithromycin Antibiotic from Aqueous Solution

Hydrogen peroxide catalytic activation holds great promise in the treatment of persistent pollutants. In this study, the novel Mn-Acacair/Al, Mn-Acacarg/Al and Mn-BTCarg/Al catalysts, supported on Al2O3, were applied for rapid hydrogen peroxide activation and azithromycin antibiotic removal. The catalysts were prepared by the calcination-hydrothermal method under air or argon atmosphere. The characterization confirmed that the modification of manganese with acetylacetonate and benzene-1,3,5-tricarboxylic acid (H3BTC) O-donor ligands highly improves the catalyst porosity, amorphousity, and abundance of coordinately unsaturated sites, which facilitate the generation of reactive oxygen species. The hydrogen peroxide activation and azithromycin removal reached 98.4% and 99.3% after 40 min using the Mn-BTCarg/Al catalyst with incredible stability and reusability. Only a 5.2% decrease in activity and less than 2% manganese releasing in solutions were detected after five regeneration cycles under the optimum operating conditions. The removal intermediates were identified by LC-MS/MS analysis, and the pathways were proposed. The hydroxylation and decarboxylation reactions play a key role in the degradation reaction.

Catalytic activation of formic acid using Pd nanocluster decorated graphitic carbon nitride for diclofenac reductive hydrodechlorination

Halogenated pharmaceuticals exhibit high toxicity if released to natural environment, and dehalogenation is a key process for their degradation. In this study, a reductive and directional dehalogenation technique, heterogenous formic acid (HCOOH) catalytic activation system, was proposed for diclofenac (DCF) dechlorination and detoxification. A functional material of Pd nanocluster decorated graphitic carbon nitride (Pd/g-C3N4) was developed for HCOOH activation. Although the optimized material (Pd1/g-C3N4) showed lower HCOOH decomposition rate (k1 = 0.287 ± 0.017 min−1) than the pristine Pd particles (k1 = 0.401 ± 0.031 min−1), it processed higher DCF degradation efficiency (97.9% within 30 min) than Pd particles. The enhancement mechanism was revealed by both experiments and theoretical calculations. Firstly, the six-fold cavities of g-C3N4 acted as anchor sites, which offered strong coordination environment for Pd nanoclusters. Secondly, the strong coordination environment of Pd led to upshifted d-band center of Pd 4d with enhanced bonding state, and then promoted HCOOH adsorption on Pd/g-C3N4, thus facilitating HCOOH decomposition through formate pathway rather than carboxyl pathway. Thirdly, Pd/g-C3N4 ensured HCOOH selectively decomposed as dehydrogenation reaction, which generated more H* (adsorbed H on Pd) than the dehydration reaction. The H* was proved to be the dominant reductive species for DCF hydrodechlorination. Moreover, the toxicities of DCF dechlorination products were greatly reduced.

Catalytic activation of peroxydisulfate by secondary mineral derived self-modified iron-based composite for florfenicol degradation: Performance and mechanism

The advanced oxidation processes (AOPs) driven by iron-based materials are the highly efficient technology for refractory organic pollutants treatment. In this work, self-modified iron-based catalysts were prepared using secondary mineral as the precursor by one-step pyrolysis process without additional dopants. The prepared catalysts exhibited excellent performance in catalytic degradation of florfenicol (FF), especially C-AJ, which was derived from ammoniojarosite [(NH4, H3O)Fe3(OH)6(SO4)2], activated PDS to degrade 93% FF with initial concentration of 50 mg/L. Quenching tests and electron paramagnetic resonance (ESR) studies showed that SO4•−, •OH, and •O2− were the main reactive species for FF degradation and their contribution degree was SO4•− > •OH > •O2−. The Fe0 and the cycle of Fe(II)/Fe(III) both contributed to the PDS activation, and the reduction of Fe(III) to Fe(II) was accelerated by S2− on the catalyst surface. In addition, Fe3O4 on the C-AJ indirectly catalyzes PDS by promoting electron transfer. The effects of catalyst dosage, PDS concentration, pH, inorganic anions, and real aqueous matrices on FF degradation, TOC analysis, and cycling test were investigated. The results showed that iron-based catalysts have superior environmental durability due to their excellent catalytic properties in the real aqueous matrices with common inorganic anions and pH 3–9 and its steady catalytic capacity with multiple cycles. Overall, this study sheds new light on the rational design of self-modified iron-based composite and develops low-cost technology toward remediation of FF-contaminated wastewater.

Heterogeneous catalytic activation of persulfate for the removal of rhodamine B and diclofenac pollutants from water using iron-impregnated biochar derived from the waste of black seed pomace

Waste reutilization in environmental remediation is highly desired as a new strategy in the scientific community for environmental applications. Industrial biowaste has been used significantly to produce biochar, which can be used in environmental remediation. In this study, a low-cost iron-impregnated modified biochar (FeBS800) was successfully prepared using a one-step pyrolysis method with waste black seed pomace as a “waste-to-resource” strategy and applied to activate peroxydisulfate (PDS) for the degradation and mineralization of rhodamine B (RhB) and diclofenac (DCF) in water. The physicochemical properties of the FeBS800 catalyst were investigated by various characterization analytical methods. The developed FeBS800 catalyst exhibits excellent catalytic activity and good stability in PDS activation. In the FeBS800/PDS system, the degradation efficiency within 10 min reached up to 98.2 % and 88.3 %, while the mineralization efficiencies within 30 min reached 48 % and 68.7 % for 20 mg/L RhB and DCF, respectively, with slight iron ions leaching of less than 3 mg/L. The optimum removal conditions of the FeBS800/PDS system were found to be 1.5 g/L catalyst dose and 10 mM PDS initial concentration at circumneutral pH solution. Moreover, the radical quenching experiment revealed that the main reactive oxygen species (ROS) responsible for the pollutants’ degradation in FeBS800/PDS system are in the order of 1O2 > •OH > O2•- > SO4•-, while singlet oxygen plays a leading role. The degradation kinetics of both pollutants (RhB and DCF) were well-fitted to the pseudo-first-order model. Furthermore, a possible mechanism pathway of PDS activation for generation ROS in the FeBS800/PDS system was proposed. Overall, the research results suggested that the modified FeBS800 could have a promising potential in activating PDS for the removal of refractory organic pollutants from water.

Current Progress on Methods and Technologies for Catalytic Methane Activation at Low Temperatures.

Methane (CH4 ) is an attractive energy source and important greenhouse gas. Therefore, from the economic and environmental point of view, scientists are working hard to activate and convert CH4 into various products or less harmful gas at low-temperature. Although the inert nature of CH bonds requires high dissociation energy at high temperatures, the efforts of researchers have demonstrated the feasibility of catalysts to activate CH4 at low temperatures. In this review, the efficient catalysts designed to reduce the CH4 oxidation temperature and improve conversion efficiencies are described. First, noble metals and transition metal-based catalysts are summarized for activating CH4 in temperatures ranging from 50 to 500°C. After that, the partial oxidation of CH4 at relatively low temperatures, including thermocatalysis in the liquid phase, photocatalysis, electrocatalysis, and nonthermal plasma technologies, is briefly discussed. Finally, the challenges and perspectives are presented to provide a systematic guideline for designing and synthesizing the highly efficient catalysts in the complete/partial oxidation of CH4 at low temperatures.

Directional growth of quasi-2D Cu2O monocrystals on rGO membranes in aqueous environments.

The preparation technology of unconventional low-dimensional Cu2O monocrystals, which exhibit specific crystal planes and present significantly unique interfacial and physicochemical properties, is attracting increasing attention and interest. Herein, by integrating a high-temperature oxidation process under vacuum and a pure-water incubation process under ambient conditions, we propose the self-assembled growth and synthesis of quasi-two-dimensional Cu2O monocrystals on reduced graphene oxide (rGO) membranes. The prepared Cu2O crystals have a single (110) crystal plane, regular rectangular morphology, and potentially well conductivity. Experimental and theoretical results suggest that this assembly is attributed to the pre-nucleation clusters aggregation and directional attachment of Cu and O on the rGO membranes in aqueous environment and cation-π interactions between the (110) crystal plane of Cu2O and rGO surface. Our findings offer a potential avenue for the discovery and design of advanced low-dimensional single-crystal materials with specific interfacial properties in a pure aqueous environment.

Functional dynamics of SARS-CoV-2 3C-like protease as a member of clan PA.

The online version contains supplementary material available at 10.1007/s12551-022-01020-x.