Rate-limiting Step Research Articles

Catalytic hydrogenation of CO2 to DME on surface Cu via highly efficient electron redistribution at the Cu0/Cu+ interface

The activity of copper-based bifunctional catalysts for CO2 hydrogenation to dimethyl ether (DME) is generally constrained by the loss of Cu0 sites during the reaction. Previous studies have focused on introducing additional elements to improve the stability of active sites. In this study, an electron redistribution of the Cu/Cu2O interface was constructed. Surface Cu0 provides active sites for H2 adsorption and dissociation, and the Cu0/Cu+ interface sites are more beneficial for the activation and hydrogenation of CO2. The Ointer–H moieties that form at interface sites reduce the reaction energy barrier of CH3OH synthesis, and the decomposition of H2COOH* to CH2O* species is the rate-limiting step. In addition, the Cu0/Cu+ interface restricts the migration of copper species and protects the weak acid sites of HZSM-5 during the reaction. The present work provides an atomic-level description of H2 dissociation and CO2 activation by Cu0/Cu+ surface and interface sites.

Deep Electron Redistributions Induced by Dual Junctions Facilitating Electroreduction of Dilute Nitrate to Ammonia.

The electronic states of metal catalysts can be redistributed by the rectifying contact between metal and semiconductor e.g., N-doped carbon (NC), while the interfacial regulation degree is very limited. Herein, a deep electronic state regulation is achieved by constructing a novel double-heterojunctional Co/Co3O4@NC catalyst containing Co/Co3O4 and Co3O4/NC heterojunctions. When used for dilute electrochemical NO3 - reduction reaction (NO3RR), the as-prepared Co/Co3O4@NC exhibits an outstanding Faradaic efficiency for NH3 formation (FENH3) of 97.9%, -0.4V versus RHE and significant NH3 yield of 303.5mmol h-1 gcat -1 at -0.6V at extremely low nitrate concentrations (100ppm NO3 --N). Experimental and theoretical results reveal that the dual junctions of Co/Co3O4 and Co3O4/NC drive a unidirectional electron transfer from Co to NC (Co→Co3O4→NC), resulting in electron-deficient Co atoms. The electron-deficient Co promotes NO3 - adsorption, the rate-determining step (RDS) for NO3RR, facilitating the dilute NO3RR to NH3. The design strategy provides a novel reference for unidirectional multistage regulation of metal electronic states boosting electrochemical dilute NO3RR, which opens up an avenue for deep electronic state regulation of electrocatalyst breaking the limitation of the electronic regulation degree by rectifying contact.

Dithienylethene-Based Photoswitchable Phosphines for the Palladium-Catalyzed Stille Coupling Reaction.

Homogeneous transition metal catalysis is a constantly developing field in chemical sciences. A growing interest in this area is photoswitchable catalysis, which pursues in situ modulation of catalyst activity through noninvasive light irradiation. Phosphorus ligands are excellent targets to accomplish this goal by introducing photoswitchable moieties; however, only a limited number of examples have been reported so far. In this work, we have developed a series of palladium complexes capable of catalyzing the Stille coupling reaction that contain photoisomerizable phosphine ligands based on dithienylethene switches. Incorporation of electron-withdrawing substituents into these dithienylethene moieties allows variation of the electron density on the phosphorus atom of the ligands upon light irradiation, which in turn leads to a modulation of the catalytic properties of the formed complexes and their activity in a model Stille coupling reaction. These results are supported by theoretical computations, which show that the energy barriers for the rate-determining steps of the catalytic cycle decrease when the photoswitchable phosphine ligands are converted to their closed state.

Tailoring Oxygen Reduction Reaction Kinetics of Fe-N-C Catalyst via Spin Manipulation for Efficient Zinc-Air Batteries.

The interaction between oxygen species and metal sites of various orbitals exhibits intimate correlation with the oxygen reduction reaction (ORR) kinetics. Herein, a new approach for boosting the inherent ORR activity of atomically dispersed Fe-N-C matrix is represented by implanting Featomic clusters nearby. The as-prepared catalyst delivers excellent ORR activity with half-wave potentials of 0.78 and 0.90V in acidic and alkaline solutions, respectively. The decent ORR activity can also be validated from the high-performance rechargeable Zn-air battery. The experiments and density functional theory calculations reveal that the electron spin-state of monodispersed Fe active sites is transferred from the low spin (LS, t2g 6 eg 0) to the medium spin (MS, t2g 5 eg 1) due to the involvement of Fe atomic clusters, leading to the spin electron filling in σ∗ orbit, by which it favors OH- desorption and in turn boosts the reaction kinetics of the rate-determining step. This work paves a solid way for rational design of high-performance Fe-based single atom catalysts through spin manipulation.

Enhancing Methylene Blue Removal through Adsorption and Photocatalysis—A Study on the GO/ZnTiO3/TiO2 Composite

This study focuses on synthesizing and characterizing a graphene oxide/ZnTiO3/TiO2 (GO/ZTO/TO) composite to efficiently remove methylene blue (MB) from water, presenting a novel solution to address industrial dye pollution. GO and ZTO/TO were synthesized by the modified Hummers and sol–gel methods, respectively, while GO/ZTO/TO was prepared using a hydrothermal process. The structural and surface properties of the composite were characterized using various analytical techniques confirming the integration of the constituent materials and suitability for dye adsorption. The study revealed that GO/ZTO/TO exhibits an adsorption capacity of 78 mg g−1 for MB, with only a 15% reduction in adsorption efficiency until the fifth reuse cycle. Furthermore, the study suggests optimal adsorption near neutral pH and enhanced performance at elevated temperatures, indicating an endothermic reaction. The adsorption behavior fits the Langmuir isotherm, implying monolayer adsorption on homogeneous surfaces, and follows pseudo-second-order kinetics, highlighting chemical interactions at the surface as the rate-limiting step. The photocatalytic degradation of MB by GO/ZTO/TO follows pseudo-first-order kinetics, with a higher rate constant than that of GO alone, demonstrating the enhanced photocatalytic activity of the composite. In conclusion, GO/ZTO/TO emerges as a promising and sustainable approach for water purification, through an adsorption process and subsequent photocatalytic degradation.

Selective Hydrofunctionalization of Alkenyl Fluorides Enabled by Nickel-Catalyzed Hydrogen Atoms and Group Transfer: Reaction Development and Mechanistic Study.

Due to the unique effect of fluorine atoms, the efficient construction of high-value alkyl fluorides has attracted significant interest in modern drug development. However, enantioselective catalytic strategies for the efficient assembly of highly functionalized chiral C(sp3)-F scaffolds from simple starting materials have been underutilized. Herein, we demonstrate a nickel-catalyzed radical transfer strategy for the efficient, modular, asymmetric hydrogenation and hydroalkylation of alkenyl fluorides with primary, secondary, and tertiary alkyl halides under mild conditions. The transformation provides facile access to various structurally complex secondary and tertiary α-fluoro amide products from readily available starting materials with excellent substrate compatibility and distinct selectivity. Furthermore, the utility of this method is demonstrated by late-stage modifications and product derivatizations. Detailed mechanistic studies and DFT calculations have been conducted, showing that the rate-determining step for asymmetric hydrogenation reaction is NiH-HAT toward alkenyl fluorides and the stereo-determining step is alcohol coordination to Ni-enolates followed by a barrierless protonation. The mechanism for the asymmetric hydroalkylation reaction is also delivered in this investigation.

Substitution Effects in Aryl Halides and Amides into the Reaction Mechanism of Ullmann-Type Coupling Reactions

In this article, we present a comprehensive computational investigation into the reaction mechanism of N-arylation of substituted aryl halides through Ullmann-type coupling reactions. Our computational findings, obtained through DFT ωB97X-D/6-311G(d,p) and ωB97X-D/LanL2DZ calculations, reveal a direct relation between the previously reported experimental reaction yields and the activation energy of haloarene activation, which constitutes the rate-limiting step in the overall coupling process. A detailed analysis of the reaction mechanism employing the Activation Strain Model indicates that the strain in the substituted iodoanilines is the primary contributor to the energy barrier, representing an average of 80% of the total strain energy. Additional analysis based on conceptual Density Functional Theory (DFT) suggests that the nucleophilicity of the nitrogen in the lactam is directly linked to the activation energies. These results provide valuable insights into the factors influencing energetic barriers and, consequently, reaction yields. These insights enable the rational modification of reactants to optimize the N-arylation process.

Density Functional Theory Study on the Mechanism of Nickel-Catalyzed 3,3-Dialkynylation of 2-Aryl Acrylamides Via Double Vinylic C-H Bond Activation.

The mechanisms of Ni-catalyzed 3,3-dialkynylation of 2-aryl acrylamide have been investigated by using density functional theory calculations. The result shows that this reaction includes double alkynylation, which involves sequential key steps of vinylic C-H bond activation, successive oxidative addition, and reductive elimination, with the second C-H bond activation being the rate-determining step. C-H and N-H bond activation occurs via the concerted metalation-deprotonation mechanism. The calculations show that no transition state exists in the first reductive elimination process, and a negative free energy barrier in the second reductive elimination process though a transition state is identified, indicating that the nickel-catalyzed vinylic C(sp2)-C(sp) bond formation does not require activation energy. Z-E isomerization is the prerequisite for the second alkynylation. In addition, our spin-flip TDDFT (SF-TDDFT) computational result discloses that the actual process of Z-E isomerization occurs on the potential energy surface of the first excited singlet state S1.

Unidentical Twins: Geometrically Similar but Chemically Distinct Metal-free Sites in Boron Oxide for Methane Oxidation to HCHO, CO and CO2.

Metal-free boron-based catalysts such as boron oxide (B2O3) and boron nitride (h-BN) are promising catalysts for the methane oxidation to HCHO and CO. The B2O3 catalyst contains various probable boron sites (B1 to B6), which may be responsible for methane oxidation. In this work, we utilized density functional theory to compare two relevant geometrically identical boron sites (B2 and B4) for their reactivities. The two sites are explored in-detail for the conversion of methane to formaldehyde (M2F), carbon monoxide and carbon dioxide. The B4 site activates the methane C-H bond easily as compared to the B2 site. In M2F conversion, the rate-determining step for the B2 site is the co-activation of dioxygen and methane, whereas over the B4 site, formaldehyde formation is the rate-determining step. The computationally-determined RDS for the B4 site coincides well with the reported experiments. It is further revealed that this site also prefers the formation of CO over CO2, which is in-line with the experiments in literature. It is also shown through orbital analysis that methanol formation does not occur during methane oxidation. We employed descriptors such as condensed Fukui functions and global electrophilicity index to chemically distinct these twin sites.

In Situ Electrochemical Rapid Induction of Highly Active γ-NiOOH Species for Industrial Anion Exchange Membrane Water Electrolyzer.

Limited by the strong oxidation environment and sluggish reconstruction process in oxygen evolution reaction (OER), designing rapid self-reconstruction with high activity and stability electrocatalysts is crucial to promoting anion exchange membrane (AEM) water electrolyzer. Herein, trace Fe/S-modified Ni oxyhydroxide (Fe/S-NiOOH/NF) nanowires are constructed via a simple in situ electrochemical oxidation strategy based on precipitation-dissolution equilibrium. In situ characterization techniques reveal that the successful introduction of Fe and S leads to lattice disorder and boosts favorable hydroxyl capture, accelerating the formation of highly active γ-NiOOH. The Density Functional Theory (DFT) calculations have also verified that the incorporation of Fe and S optimizes the electrons redistribution and the d-band center, decreasing the energy barrier of the rate-determining step (*O→*OOH). Benefited from the unique electronic structure and intermediate adsorption, the Fe/S-NiOOH/NF catalyst only requires the overpotential of 345 mV to reach the industrial current density of 1000mAcm-2 for 120 h. Meanwhile, assembled AEM water electrolyzer (Fe/S-NiOOH//Pt/C-60°C) can deliver 1000mAcm-2 at a cell voltage of 2.24V, operating at the average energy efficiency of 71% for 100 h. In summary, this work presents a rapid self-reconstruction strategy for high-performance AEM electrocatalysts for future hydrogen economy.

Epidermal retinol dehydrogenases cyclically regulate stem cell markers and clock genes and influence hair composition

The hair follicle (HF) is a self-renewing adult miniorgan that undergoes drastic metabolic and morphological changes during precisely timed cyclic organogenesis. The HF cycle is known to be regulated by steroid hormones, growth factors and circadian clock genes. Recent data also suggest a role for a vitamin A derivative, all-trans-retinoic acid (ATRA), the activating ligand of transcription factors, retinoic acid receptors, in the regulation of the HF cycle. Here we demonstrate that ATRA signaling cycles during HF regeneration and this pattern is disrupted by genetic deletion of epidermal retinol dehydrogenases 2 (RDHE2, SDR16C5) and RDHE2-similar (RDHE2S, SDR16C6) that catalyze the rate-limiting step in ATRA biosynthesis. Deletion of RDHEs results in accelerated anagen to catagen and telogen to anagen transitions, altered HF composition, reduced levels of HF stem cell markers, and dysregulated circadian clock gene expression, suggesting a broad role of RDHEs in coordinating multiple signaling pathways.

First Principles Study of the Structure–Performance Relation of Pristine Wn+1Cn and Oxygen-Functionalized Wn+1CnO2 MXenes as Cathode Catalysts for Li-O2 Batteries

Li-O2 batteries are considered a highly promising energy storage solution. However, their practical implementation is hindered by the sluggish kinetics of the oxygen reduction (ORR) and oxygen evolution (OER) reactions at cathodes during discharging and charging, respectively. In this work, we investigated the catalytic performance of Wn+1Cn and Wn+1CnO2 MXenes (n = 1, 2, and 3) as cathodes for Li-O2 batteries using first principles calculations. Both Wn+1Cn and Wn+1CnO2 MXenes show high conductivity, and their conductivity is further enhanced with increasing atomic layers, as reflected by the elevated density of states at the Fermi level. The oxygen functionalization can change the electronic properties of WC MXenes from the electrophilic W surface of Wn+1Cn to the nucleophilic O surface of Wn+1CnO2, which is beneficial for the activation of the Li-O bond, and thus promotes the Li+ deintercalation during the charge–discharge process. On both Wn+1Cn and Wn+1CnO2, the rate-determining step (RDS) of ORR is the formation of the (Li2O)2* product, while the RDS of OER is the LiO2* decomposition. The overpotentials of ORR and OER are positively linearly correlated with the adsorption energy of the RDS LixO2* intermediates. By lowering the energy band center, the oxygen functionalization and increasing atomic layers can effectively reduce the adsorption strength of the LixO2* intermediates, thereby reducing the ORR and OER overpotentials. The W4C3O2 MXene shows immense potential as a cathode catalyst for Li-O2 batteries due to its outstanding conductivity and super-low ORR, OER, and total overpotentials (0.25, 0.38, and 0.63 V).

Effect of Facet on Local Electron Density of Oxygen Vacancy in Catalysts for Nitrogen Electro-Reduction.

Oxygen-vacancy (Ov) engineering is an effective strategy to manipulate the electronic configuration of catalysts for electrochemical nitrogen reduction reaction (eNRR). The influence of the stable facet on the electronic configuration of Ov is widely studied, however, the effect of the reactive facet on the local electron density of Ov is unveiled. In this work, an eNRR electrode R(111)-TiO2/HGO is provided with a high proportion exposed reactive facet (111) of rutile-TiO2 (denoted as R(111)-TiO2) nanocrystals with Ov anchored in hierarchically porous graphite oxide (HGO) nanofilms. The R(111)-TiO2/HGO exhibits excellent eNRR performance with an NH3 yield rate of 20.68 µg h-1 cm-2, which is ≈20 times the control electrode with the most stable facet (110) exposed (R(110)-TiO2/HGO). The experimental data and theoretical simulations reveal that the crystal facet (111) has a positive effect on regulating the local electron density around the oxygen vacancy and the two adjacent Ti-sites, promoting the π-back-donation, minimizing the eNRR barrier, and transforming the rate determination step to *NNH→*NNHH. This work illuminates the effect of crystal facet on the performance of eNRR, and offers a novel strategy to design efficient eNRR catalysts.

Evaluation of Fusobacterium nucleatum Enoyl-ACP Reductase (FabK) as a Narrow-Spectrum Drug Target.

Fusobacterium nucleatum, a pathobiont inhabiting the oral cavity, contributes to opportunistic diseases, such as periodontal diseases and gastrointestinal cancers, which involve microbiota imbalance. Broad-spectrum antimicrobial agents, while effective against F. nucleatum infections, can exacerbate dysbiosis. This necessitates the discovery of more targeted narrow-spectrum antimicrobial agents. We therefore investigated the potential for the fusobacterial enoyl-ACP reductase II (ENR II) isoenzyme FnFabK (C4N14_ 04250) as a narrow-spectrum drug target. ENRs catalyze the rate-limiting step in the bacterial fatty acid synthesis pathway. Bioinformatics revealed that of the four distinct bacterial ENR isoforms, F. nucleatum specifically encodes FnFabK. Genetic studies revealed that fabK was indispensable for F. nucleatum growth, as the gene could not be deleted, and silencing of its mRNA inhibited growth under the test conditions. Remarkably, exogenous fatty acids failed to rescue growth inhibition caused by the silencing of fabK. Screening of synthetic phenylimidazole analogues of a known FabK inhibitor identified an inhibitor (i.e., 681) of FnFabK enzymatic activity and F. nucleatum growth, with an IC50 of 2.1 μM (1.0 μg/mL) and a MIC of 0.4 μg/mL, respectively. Exogenous fatty acids did not attenuate the activity of 681 against F. nucleatum. Furthermore, FnFabK was confirmed as the intracellular target of 681 based on the overexpression of FnFabK shifting MICs and 681-resistant mutants having amino acid substitutions in FnFabK or mutations in other genetic loci affecting fatty acid biosynthesis. 681 had minimal activity against a range of commensal flora, and it was less active against streptococci in physiologic fatty acids. Taken together, FnFabK is an essential enzyme that is amenable to drug targeting for the discovery and development of narrow-spectrum antimicrobial agents.

Exploration of Streptomyces fradiae J1-021 as a Potential Host for the Heterologous Production of Spinosad.

Spinosad is a potent insecticide produced by Saccharopolyspora spinosa. However, it harbors certain limitations of a low growing rate and unfeasible genetic manipulation that can be overcome by adopting a superior platform, such as Streptomyces. Herein, we exploited the industrial tylosin-producing Streptomyces fradiae J1-021 for the heterologous production of spinosad. An engineered strain (HW01) with deletion of the tylosin biosynthetic gene cluster (BGC) was constructed and then transformed with the natural spinosad BGC. The distribution and expression levels of the tylosin BGC operons were assessed to construct a natural promoter library. The rate-limiting steps of spinosad biosynthesis were identified by analyzing the transcriptional expression of the spinosad biosynthetic genes. The stepwise engineering work involved the overexpression of the biosynthetic genes participating in rate-limiting pathways using strong promoters, affording an increase in spinosad production to 112.4 μg/L. These results demonstrate that strain HW01 has the potential to be used as a chassis for the heterologous production of polyketides.

Ruthenium(II)-Catalyzed Oxidative Annulation of Imidazo[1,5-a]quinolin-2-iums Salts and Internal Alkynes via C-H Bond Activation.

Ruthenium(II)-catalyzed synthesis of π-conjugated fused imidazo[1,5-a]quinolin-2-ium derivatives have been achieved via C-H activation of quinoline-functionalized NHC (NHC = N-heterocyclic carbene) and oxidative coupling with internal alkynes. The reaction occurred with high efficiency, broad substrate scope, tolerates a wide range of functional groups and utilized into a gram-scale. Synthetic applications of a coupled product have been exemplified in the late-stage derivatization of various highly functionalized scaffolds. Moreover, most of the annulated products exhibit intense fluorescence and have potential applications in optoelectronic devices. Mechanistic studies have provided insights into the spectroscopic characterization of key five-membered ruthenacycle intermediate and Ru(0) sandwich species. Based on several control experiments, deuterium-kinetic isotope effect, and thermodynamic activation parameters the mechanistic finding demonstrated that fused imidazo-[1,5-a]quinolin-2-ium C(2)-H bond cleavage is the rate-determining step and ruling out the possibility of reductive elimination for controlling the rate of reaction.

Copper-catalysed asymmetric hydroboration of alkenes with 1,2-benzazaborines to access chiral naphthalene isosteres.

Bioisosteric replacement has emerged as a clear strategy for drug-structure optimization. Naphthalene is the core element of many chiral pharmaceuticals and drug candidates. However, as a promising isostere of naphthalene, the chiral version of 1,2-benzazaborine has rarely been explored due to the lack of efficient synthetic methods. Here we describe a copper-catalysed enantioselective hydroboration of alkenes with 1,2-benzazaborines. The method provides a general platform for the atom-economic and efficient construction of diverse chiral 1,2-benzazaborine compounds (more than 60 examples) that bear a 2-carbon-stereogenic centre or allene skeleton in high yields and excellent enantioselectivities. Three 1,2-benzazaborine analogues of bioactive chiral naphthalene-containing molecules have been prepared, and a series of transformations around chiral 1,2-benzazaborines have also been developed. Notably, the hydroboration process of this study reveals that the identity of 1,2-benzazaborine plays an essential role in the rate-determining step and catalyst resting state.

Mechanistic aspects of Pd-catalyzed ethylene decomposition in vinyl acetate synthesis

Vinyl acetate has a broad range of applications in the market. However, the side reactions of ethylene decomposition and CO2 formation have a significant effect on the selectivity of vinyl acetate synthesis. In this study, a comprehensive reaction network was calculated by the density functional theory (DFT) method to understand the mechanism of the side reactions. The DFT results indicated that the C-H bond is easier to break than C-C bond except for CCH species during ethylene decomposition on the Pd (100) surface. The introduction of Au on the alloy surface inhibits the decomposition of ethylene, which improves the selectivity of the reaction. The adsorbed O atom inhibits the first three dehydrogenation of ethylene but promotes the CCH species dehydrogenation. The pathway for the decomposition of ethylene is: CH2CH2 → CHCH2 → CHCH → CCH → C+CH, and the C-C bond cleavage of CCH is identified as the rate-determining step. The rate-determining step for CO2 formation is the combination of carbon and oxygen atoms to produce CO, and the alloy surface presents a high energy barrier, hindering CO2 production. This study presents a further mechanistic insight into ethylene decomposition and CO2 formation, which has implications for the control of side reactions in vinyl acetate synthesis.

Allosteric activation unveils protein-mass modulation of ATP phosphoribosyltransferase product release

Heavy-isotope substitution into enzymes slows down bond vibrations and may alter transition-state barrier crossing probability if this is coupled to fast protein motions. ATP phosphoribosyltransferase from Acinetobacter baumannii is a multi-protein complex where the regulatory protein HisZ allosterically enhances catalysis by the catalytic protein HisGS. This is accompanied by a shift in rate-limiting step from chemistry to product release. Here we report that isotope-labelling of HisGS has no effect on the nonactivated reaction, which involves negative activation heat capacity, while HisZ-activated HisGS catalytic rate decreases in a strictly mass-dependent fashion across five different HisGS masses, at low temperatures. Surprisingly, the effect is not linked to the chemical step, but to fast motions governing product release in the activated enzyme. Disruption of a specific enzyme-product interaction abolishes the isotope effects. Results highlight how altered protein mass perturbs allosterically modulated thermal motions relevant to the catalytic cycle beyond the chemical step.

Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity

Improving the kinetics and selectivity of CO2/CO electroreduction to valuable multi-carbon products is a challenge for science and is a requirement for practical relevance. Here we develop a thiol-modified surface ligand strategy that promotes electrochemical CO-to-acetate. We explore a picture wherein nucleophilic interaction between the lone pairs of sulfur and the empty orbitals of reaction intermediates contributes to making the acetate pathway more energetically accessible. Density functional theory calculations and Raman spectroscopy suggest a mechanism where the nucleophilic interaction increases the sp2 hybridization of CO(ad), facilitating the rate-determining step, CO* to (CHO)*. We find that the ligands stabilize the (HOOC–CH2)* intermediate, a key intermediate in the acetate pathway. In-situ Raman spectroscopy shows shifts in C–O, Cu–C, and C–S vibrational frequencies that agree with a picture of surface ligand-intermediate interactions. A Faradaic efficiency of 70% is obtained on optimized thiol-capped Cu catalysts, with onset potentials 100 mV lower than in the case of reference Cu catalysts.