Fast Catalysis Research Articles

Significant enhancement in treatment of salty wastewater by pre-magnetization Fe0/H2O2 process

Nowadays, Fenton (Fe2+/H2O2) process is increasingly applied to wastewater treatment, however, the treatment efficiency would be inhibited largely when treated salty wastewater. To overcome this limitation, pre-magnetization (pre-magn-Fe0)/H2O2 process was investigated to treat salty wastewater, which could enhance the degradation rate of organic pollutants (1.2–171.2 folds enhancement) and reduce reagents dosage (save 75% H2O2) in salty system compared with Fe0/H2O2 process, using Orange G as the target pollutant and Na2SO4 as the model salty system. The characterizations by SEM, XRD and XPS and the intensity of DMPO–OH adduct signals in different processes confirmed this enhancement attributed to the increase of corrosion of Fe0 inducing fast catalysis of H2O2 and generation of hydroxyl radicals. Pre-magn-Fe0/H2O2 process could also have 5.9, 26.4 and 93.7 folds enhancement in NaCl, NaNO3 and Na2HPO4 salty system, respectively. Meanwhile, pre-magn-Fe0/H2O2 process could keep close performance in Na2SO4 and NaCl salty systems and have better performance in NaNO3 and Na2HPO4 salty systems than Fenton process. Pre-magn-Fe0/H2O2 process also had remarkable improvement (1.1–5.3 folds) on the removal of many refractory contaminants in salty system. Furthermore, it could also keep good performance in real reverse osmosis concentrated wastewater and petrochemical wastewater. Therefore, pre-magn-Fe0/H2O2 process is a more cost-effective process to treat salty wastewater, which could have not only improved performance than conventional system and Fe0/H2O2 process, but also good performance as Fenton process.

Nitrogen-doped microporous carbon: An efficient oxygen reduction catalyst for Zn-air batteries

Abstract N-doped microporous carbon as an exceptional metal-free catalyst from waste biomass (banana peel as representative) was obtained via fast catalysis carbonization, followed by N-doping modification. The method achieves a relatively high C conversion efficiency of ∼41.9%. The final carbon materials are doped by N (∼3 at.%) and possess high surface area (∼1097 m2 g−1) and abundant micropores. Compared to commercial Pt/C materials, the as-prepared carbon catalyst exhibits a comparable electrocatalytic activity and much better stability. Furthermore, the metal-free catalyst loaded Zn-air battery possesses higher discharge voltage and power density as compared with that of commercial Pt/C. This novel technique can also be readily applied to produce metal-free carbon catalysts from other typical waste biomass (e.g., orange peel, leaves) as the carbon sources. The method can be developed as a potentially general and effective industrial route to transform waste biomass into high value-added microporous carbon with superior functionalities.

Development of enzyme-loaded PVA microspheres by membrane emulsification

Enzyme applications have a considerable role at the heart of biotechnological processes. A large number of these biotechnological processes require successful enzyme immobilization in terms of resistance to leaking, retention of enzyme activity over long-term storage, operational stability under adverse environmental conditions, accessibility to substrates, fast catalysis, and, in general, proper enzyme immobilization density with adequate orientation. Among the different methods of immobilization, enzyme encapsulation in a network matrix of polymeric materials in the form of particles is of particular interest. Polyvinyl alcohol (PVA) microspheres produced by a membrane emulsification/cross-linking method have been used as enzyme carriers. The enzyme was immobilized during particle formation (by entrapment) or after particle production (by adsorption and cross-linking). The entrapment during particle solidification from a water in oil (W/O) emulsion, allowed the enzyme to be distributed at the interface in its active form. The best operating conditions to control particle size, particle size distribution and particle structure for PVA microspheres production as well as the most suitable method for lipase immobilization on/in PVA microspheres have been identified. The immobilization method that does not affect enzyme intrinsic biocatalytic activity, whilst allowing at the same time confinement with balance between molecular mobility and heterogenization has been identified.

Human sterol 14α-demethylase as a target for anticancer chemotherapy: towards structure-aided drug design

Rapidly multiplying cancer cells synthesize greater amounts of cholesterol to build their membranes. Cholesterol-lowering drugs (statins) are currently in clinical trials for anticancer chemotherapy. However, given at higher doses, statins cause serious side effects by inhibiting the formation of other biologically important molecules derived from mevalonate. Sterol 14α-demethylase (CYP51), which acts 10 steps downstream, is potentially a more specific drug target because this portion of the pathway is fully committed to cholesterol production. However, screening a variety of commercial and experimental inhibitors of microbial CYP51 orthologs revealed that most of them (including all clinical antifungals) weakly inhibit human CYP51 activity, even if they display high apparent spectral binding affinity. Only one relatively potent compound, (R)-N-(1-(3,4'-difluorobiphenyl-4-yl)-2-(1H-imidazol-1-yl)ethyl)-4-(5-phenyl-1,3,4-oxadiazol-2-yl)benzamide (VFV), was identified. VFV has been further tested in cellular experiments and found to decrease proliferation of different cancer cell types. The crystal structures of human CYP51-VFV complexes (2.0 and 2.5 Å) both display a 2:1 inhibitor/enzyme stoichiometry, provide molecular insights regarding a broader substrate profile, faster catalysis, and weaker susceptibility of human CYP51 to inhibition, and outline directions for the development of more potent inhibitors.

Oxygen content modulation by nanoscale chemical and electrical patterning in epitaxial SrCoO3−δ (0 < δ ≤ 0.5) thin films

Fast controllable redox reactions in solid materials at room temperature are a promising strategy for enhancing the overall performance and lifetime of many energy technology materials and devices. Easy control of oxygen content is a key concept for the realisation of fast catalysis and bulk diffusion at room temperature. Here, high quality epitaxial brownmillerite SrCoO2.5 thin films have been oxidised to perovskite (P) SrCoO3 with NaClO. X-ray diffraction, scanning probe microscopy and x-ray photoelectron spectroscopy measurements were performed to investigate the structural and electronic changes of the material. The oxidised thin films were found to exhibit distinct morphological changes from an atomically flat terrace structure to forming small nanosized islands with boundaries preferentially in [100] or [010] directions all over the surface, relaxing the in-plane strain imposed by the substrate. The conductivity, or oxygen content, of each single island is confined by these textures, which can be locally patterned even further with electric poling. The high charging level at the island boundaries indicates a magnified electric capacity of SCO thin films, which could be exploited in future device geometries. This finding represents a new way of oxygen modulation with associated self-assembled charge confinement to nanoscale boundaries, offering interesting prospects in nanotechnology applications.

Accounting for the Dynamic Oxidative Behavior of Nickel Anodes.

The dynamic behavior of the anodic peak for amorphous nickel oxy/hydroxide (a-NiOx) films in basic media was investigated. Chronocoulometry of films with known nickel concentrations reveals that a total of four electrons per nickel site comprise the signature anodic peak at 1.32 V during the first oxidative scan, and two electrons are passed through the associated cathodic peak on the reverse scan. The anodic and cathodic signals each contain two electrons on the successive scans. Catalytic oxygen evolution reaction (OER) was detected within the anodic peak, which is at a lower potential than is widely assumed. In order to rationalize these experimental results, we propose that the four-electron oxidation event is the conversion of the film from nickel(II) hydroxide ([Ni(II)-OH](-)) to a higher valent nickel peroxide species (e.g., Ni(IV)-OO or Ni(III)-OO·). The subsequent reduction of the nickel peroxide species is confined by a chemical step resulting in the accumulation of [Ni(II)-OOH](-), which is then oxidized by two electrons to form Ni(IV)-OO during the subsequent oxidative scan on the time scale of a cyclic voltammetric experiment. Our proposed mechanism and the experimental determination that each nickel site is oxidized by four electrons helps link the myriad of seemingly disparate literature data related to OER catalysis by nickel electrodes. The faster catalysis that occurs at higher oxidative potentials is derived from a minority species and is not elaborated here.

Electrophilic activation of alkynes for enyne cycloisomerization reactions with in situ generated early/late heterobimetallic Pt-Ti catalysts.

In situ formation of heterobimetallic Pt-Ti catalysts enables rapid room temperature catalysis in enyne cycloisomerization reactions. The Lewis acidic titanium atom in the ligand framework is shown to be essential for fast catalysis. A range of enyne substrates are efficiently cyclized to carbocycles and heterocycles in high yield.

Cyclic Voltammetry of Electrocatalytic Films: Fast Catalysis Regimes

AbstractUnderstanding how electrocatalytic films function is of considerable current interest in view of modern energy and analytical challenges. Application of cyclic voltammetry to the analysis of these systems is a worthy alternative to steady‐state techniques in terms of simplicity and rapidity of the current–potential curve recording and the larger extent by which the rate of substrate diffusion may be varied through the rate of potential scanning. The interplay between catalytic reaction, diffusive permeation of the substrate, and diffusion‐like transport of charge is analyzed for fast catalytic reactions as a function of two dimensionless parameters. Procedures for determining the kinetic constants that govern the responses and, particularly, the rate of the catalytic reaction, ensue, based upon on the variations observed when changing scan rate, substrate concentration, and film thickness. These analyses also provide a basis for rational benchmarking of catalysts.

Kinetic and mechanistic studies of the reactivity of iron(IV) TAMLs toward organic sulfides in water: resolving a fast catalysis versus slower single-turnover reactivity dilemma

TAML complex is oxidized by H2O2 or tBuOOH in water at pH < 10 into the corresponding iron(IV) μ-oxo-bridged dimer 2, which oxidizes readily ring-substituted thioanisoles p-XC6H4SMe (X=H, MeO, Me, Cl, CN) into the corresponding sulfoxides with regeneration of 1. The oxidation studied under pseudo-first-order conditions using the stopped-flow technique by monitoring the fading of the 420-nm band of 2 follows hyperbolic kinetics according to the rate law kobs = ab[p-XC6H4SMe]/(1 + b[p-XC6H4SMe]) at pH 8 and 25 °C. Parameters a, b, and ab all decrease for electron-poorer thioanisoles and the Hammett value ρ ~ 1 has been found for ab, which can be associated with the second-order rate constants for oxidation of thioanisoles by 2. The kinetics of oxidation of p-NO2C6H4SMe by H2O2 catalyzed by 1 has been studied under steady-state conditions. Covering the concentration of 1 in a 100-fold range has revealed that though first-order kinetics in 1 is observed at low catalyst concentrations (below 10−6 M), there is a significant negative deviation from linearity at [1] > 10−6 M. The latter was rationalized by the equilibrium between the monomeric and dimeric FeIV species 2 M ⇌ M–M (Kd), both being able to oxidize p-NO2C6H4SMe with rate constants km and kd which were found to be (13 ± 1) × 104 and (0.32 ± 0.01) × 104 M−1 s−1, respectively. The difference in the rate constants is the key for resolving the dilemma of faster catalysis versus slower single-turnover reactivity of TAML activators in water.

Origin of fast catalysis in allylic amination reactions catalyzed by Pd-Ti heterobimetallic complexes.

Experiments and density functional calculations were used to quantify the impact of the Pd-Ti interaction in the cationic heterobimetallic Cl2Ti(N(t)BuPPh2)2Pd(η(3)-methallyl) catalyst 1 used for allylic aminations. The catalytic significance of the Pd-Ti interaction was evaluated computationally by examining the catalytic cycle for catalyst 1 with a conformation where the Pd-Ti interaction is intact versus one where the Pd-Ti interaction is severed. Studies were also performed on the relative reactivity of the cationic monometallic (CH2)2(N(t)BuPPh2)2Pd(η(3)-methallyl) catalyst 2 where the Ti from catalyst 1 was replaced by an ethylene group. These computational and experimental studies revealed that the Pd-Ti interaction lowers the activation barrier for turnover-limiting amine reductive addition and accelerates catalysis up to 10(5). The Pd-Ti distance in 1 is the result of the N(t)Bu groups enforcing a boat conformation that brings the two metals into close proximity, especially in the transition state. The turnover frequency of classic Pd π allyl complexes was compared to that of 1 to determine the impact of P-Pd-P coordination angle and ligand electronic properties on catalysis. These experiments identified that cationic (PPh3)2Pd(η(3)-CH2C(CH3)CH2) catalyst 3 performs similarly to 1 for allylic aminations with diethylamine. However, computations and experiment reveal that the apparent similarity in reactivity is due to very fast reaction kinetics. The higher reactivity of 1 versus 3 was confirmed in the reaction of methallyl chloride and 2,2,6,6-tetramethylpiperidine (TMP). Overall, experiments and calculations demonstrate that the Pd-Ti interaction induces and is responsible for significantly lower barriers and faster catalysis for allylic aminations.

Rh–POP Pincer Xantphos Complexes for C–S and C–H Activation. Implications for Carbothiolation Catalysis

The neutral Rh(I)–Xantphos complex [Rh(κ3-P,O,P-Xantphos)Cl]n, 4, and cationic Rh(III) [Rh(κ3-P,O,P-Xantphos)(H)2][BArF4], 2a, and [Rh(κ3-P,O,P-Xantphos-3,5-C6H3(CF3)2)(H)2][BArF4], 2b, are described [ArF = 3,5-(CF3)2C6H3; Xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; Xantphos-3,5-C6H3(CF3)2 = 9,9-dimethylxanthene-4,5-bis(bis(3,5-bis(trifluoromethyl)phenyl)phosphine]. A solid-state structure of 2b isolated from C6H5Cl solution shows a κ1-chlorobenzene adduct, [Rh(κ3-P,O,P-Xantphos-3,5-C6H3(CF3)2)(H)2(κ1-ClC6H5)][BArF4], 3. Addition of H2 to 4 affords, crystallographically characterized, [Rh(κ3-P,O,P-Xantphos)(H)2Cl], 5. Addition of diphenyl acetylene to 2a results in the formation of the C–H activated metallacyclopentadiene [Rh(κ3-P,O,P-Xantphos)(ClCH2Cl)(σ,σ-(C6H4)C(H)═CPh)][BArF4], 7, a rare example of a crystallographically characterized Rh–dichloromethane complex, alongside the Rh(I) complex mer-[Rh(κ3-P,O,P-Xantphos)(η2-PhCCPh)][BArF4], 6. Halide abstraction from [Rh(κ3-P,O,P-Xantphos)Cl]n in the presence of diphenylacetylene affords 6 as the only product, which in the solid state shows that the alkyne binds perpendicular to the κ3-POP Xantphos ligand plane. This complex acts as a latent source of the [Rh(κ3-P,O,P-Xantphos)]+ fragment and facilitates ortho-directed C–S activation in a number of 2-arylsulfides to give mer-[Rh(κ3-P,O,P-Xantphos)(σ,κ1-Ar)(SMe)][BArF4] (Ar = C6H4COMe, 8; C6H4(CO)OMe, 9; C6H4NO2, 10; C6H4CNCH2CH2O, 11; C6H4C5H4N, 12). Similar C–S bond cleavage is observed with allyl sulfide, to give fac-[Rh(κ3-P,O,P-Xantphos)(η3-C3H5)(SPh)][BArF4], 13. These products of C–S activation have been crystallographically characterized. For 8 in situ monitoring of the reaction by NMR spectroscopy reveals the initial formation of fac-κ3-8, which then proceeds to isomerize to the mer-isomer. With the para-ketone aryl sulfide, 4-SMeC 6H4COMe, C–H activation ortho to the ketone occurs to give mer-[Rh(κ3-P,O,P-Xantphos)(σ,κ1-4-(COMe)C6H3SMe)(H)][BArF4], 14. The temporal evolution of carbothiolation catalysis using mer-κ3-8, and phenyl acetylene and 2-(methylthio)acetophenone substrates shows initial fast catalysis and then a considerably slower evolution of the product. We suggest that the initially formed fac-isomer of the C–S activation product is considerably more active than the mer-isomer (i.e., mer-8), the latter of which is formed rapidly by isomerization, and this accounts for the observed difference in rates. A likely mechanism is proposed based upon these data.

A one-pot synthesis of nanostructured mesoporous TiO2 films on graphite felt substrates for fast catalysis

Crack-free mesoporous anatase films are obtained on graphite felt using a one-pot synthesis from a precursor solution. The films are characterized by high photocatalytic performance in comparison to macro-mesoporous films on silicon substrates.

Synthesis of neodymium-doped manganese dioxide via electrodeposition for fast catalysis

Neodymium (Nd) ions were successfully substituted for manganese in the crystal lattice of electrolytic amorphous nanomanganese dioxide (EAMD) for the first time, by cathodic deposition from a basic aqueous solution of KMnO4 at 22°C. The synthesized nanomaterials are characterized by XRD, SEM, TEM, HRTEM, and XPS. The Nd-doped EAMD (Nd-EAMD) produced at 5.0V is amorphous with homogeneous size and morphology with an average particle size of 26.9nm. The percent Nd substitution is about 0.69 at%. The as-prepared nanomaterials increase the rate of transformation of Rhodamine B (Rh B) in solution and proceed via an oxidative mechanism.

Identification of Minimal HDV-Like Ribozymes with Unique Divalent Metal Ion Dependence in the Human Microbiome

HDV-like self-cleaving ribozymes have been found in a wide variety of organisms, implicated in diverse biological processes, and their activity typically shows a strong divalent metal dependence, but little metal specificity. Recent studies suggested that very short variants of these ribozymes exist in nature, but their distribution and biochemical properties have not been established. To map out the distribution of small HDV-like ribozymes, the drz-Spur-3 sequence was minimized to yield a core construct for structure-based bioinformatic searches. These searches revealed several microbial ribozymes, particularly in the human microbiome. Kinetic profile of the smallest ribozyme revealed two distinct metal binding sites, only one of which promotes fast catalysis. Furthermore, this ribozyme showed markedly reduced activity in Ca(2+), even in the presence of physiological Mg(2+) concentrations. Our study substantially expands the number of microbial HDV-like ribozymes and provides an example of cleavage regulation by divalent metals.

Reversible redox reactions in an epitaxially stabilized SrCoOx oxygen sponge

Fast, reversible redox reactions in solids at low temperatures without thermomechanical degradation are a promising strategy for enhancing the overall performance and lifetime of many energy materials and devices. However, the robust nature of the cation's oxidation state and the high thermodynamic barrier have hindered the realization of fast catalysis and bulk diffusion at low temperatures. Here, we report a significant lowering of the redox temperature by epitaxial stabilization of strontium cobaltites (SrCoOx) grown directly as one of two distinct crystalline phases, either the perovskite SrCoO3-{\delta} or the brownmillerite SrCoO2.5. Importantly, these two phases can be reversibly switched at a remarkably reduced temperature (200~300 {\deg}C) in a considerably short time (< 1 min) without destroying the parent framework. The fast, low temperature redox activity in SrCoO3-{\delta} is attributed to a small Gibbs free energy difference between two topotatic phases. Our findings thus provide useful information for developing highly sensitive electrochemical sensors and low temperature cathode materials.

A Three-Stage Mechanistic Model for Ammonia–Borane Dehydrogenation by Shvo’s Catalyst

We propose a mechanistic model for three-stage dehydrogenation of ammonia borane (AB) catalyzed by Shvo's cyclopentadienone-ligated ruthenium complex. We provide evidence for a plausible mechanism for catalyst deactivation, the transition from fast catalysis to slow catalysis, and relate those findings to the invention of a second-generation catalyst that does not suffer from the same deactivation chemistry.The primary mechanism of catalyst deactivation is borazine-mediated hydroboration of the ruthenium species that is the active oxidant in the fast catalysis case. This transition is characterized by a change in the rate law for the reaction and changes in the apparent resting state of the catalyst. Also, in this slow catalysis situation, we see an additional intermediate in the sequence of boron, nitrogen species, aminodiborane. This occurs with concurrent generation of NH(3), which itself does not strongly affect the rate of AB dehydrogenation.

Tailored ligand acceleration of the Cu-catalyzed azide-alkyne cycloaddition reaction: practical and mechanistic implications.

Tris(heterocyclemethyl)amines containing mixtures of 1,2,3-triazolyl, 2-benzimidazoyl, and 2-pyridyl components were prepared for ligand acceleration of the copper-catalyzed azide-alkyne cycloaddition reaction. Two classes of ligands were identified: those that give rise to high reaction rates in coordinating solvents but inhibit the process when used in excess relative to copper and those that provide for fast catalysis in water and are not inhibitory in excess. Several "mixed" ligands were identified that performed well under both types of conditions. Kinetics measurements as a function of ligand:metal ratio and catalyst concentration were found to be consistent with an active Cu(2)L formulation. Since strongly bound chelating agents are not always the most effective, achieving optimal rates requires an assessment of the potential donor molecules in the reaction mixture. Simple rules are provided to guide the user in the choice of effective ligands and reaction conditions to suit most classes of substrates, solvents, and concentrations.

Shape-Controlled Catalysis by Cetyltrimethylammonium Bromide Terminated Gold Nanospheres, Nanorods, and Nanoprisms

Shape-controlled Au nanospheres, nanorods, and nanoprisms have been utilized for the first time for selective chemical reduction of different aromatic nitro compounds to the corresponding amino derivatives at room temperature. Careful observation reveals that the reaction was fastest with nanospheres and slowest with nanorods, whereas the rate was intermediate with nanoprisms when keeping the numbers of particles approximately the same. Controlled experiments revealed that our reaction followed the nitroso and hydroxylamine pathway. The yield of the product was very high, and the method should be applicable for very fast catalysis reaction of other nitro compounds.

Development of catalysts for fast, energy efficient post combustion capture of CO2 into water; an alternative to monoethanolamine (MEA) solvents

Abstract The aim is to develop fast catalytic absorption/desorption of CO2 at low temperatures using water as solvent. The naturally occurring zinc metallo -enzyme carbonic anhydrase (CA) can concentrate CO2 using a reversible hydration/dehydration cycle at neutral pH and at ambient temperatures. A number of macrocyclic and tripodal complexes of zinc (II), and other metals that mimic the CA catalytic process, proceed by hydration of CO2 to bicarbonate followed by the reverse dehydration of the bicarbonate to regenerate CO2. This initial study is of the fast catalysis of the reverse reaction (the dehydration of the bicarbonate ion back to CO2) at temperatures in the range 20–55 ∘C. The turnover rate constants for the catalytic desorption have been measured for zinc-1, 4, 7, 10-tetraazacyclo-dodecane, (zinc-cyclen), the zinc tripodal complexes: zinc-nitrilo-tris(2-benzimidazoyl-methyl-6-sulfonic acid), (zinc-L1S), and zinc-tris(2-benzimidazoylmethyl)-amine, (zinc -LI). CA or the zinc complexes are proposed for utilization in a water based capture process, hence avoiding the energy intensive steam stripping steps necessary with amine solvents.

Role of Induced Fit in Enzyme Specificity: A Molecular Forward/Reverse Switch

Enzyme structures solved with and without bound substrate often show that substrate-induced conformational changes bring catalytic residues into alignment, alter the local environment, and position the substrate for catalysis. Although the structural data are compelling, the role of conformational changes in enzyme specificity has been controversial in that specificity is a kinetic property that is not easy to predict based upon structure alone. Recent studies on DNA polymerization have illuminated the role of substrate-induced conformational changes in enzyme specificity by showing that the rate at which the enzyme opens to release the bound substrate is a key kinetic parameter. The slow release of a correct substrate commits it to the forward reaction so that specificity is determined solely by the rate of substrate binding, including the isomerization step, and not by the slower rate of the chemical reaction. In contrast, fast dissociation of an incorrect substrate favors release rather than reaction. Thus, the conformational change acts as a molecular switch to select the right substrate and to recognize and disfavor the reaction of an incorrect substrate. A conformational switch may also favor release rather than reverse reaction of the product.