Rate-limiting Step Research Articles

Positively Charged Hollow Co Nanoshells by Kirkendall Effect Stabilized by Electron Sink for Alkaline Water Dissociation.

While cobalt (Co) exhibits a comparable energy barrier for H* adsorption/desorption to platinum in theory, it is generally not suitable for alkaline hydrogen evolution reaction (HER) because of unfavorable water dissociation. Here, the Kirkendall effect is adopted to fabricate positive-charged hollow metal Co (PHCo) nanoshells that are stabilized by MoO2 and chainmail carbon as the electron sink. Compared to the zero-valent Co, the PHCo accelerates the water dissociation and changes the rate-determining step from Volmer to Heyrovsky process. Alkaline HER occurs with a low overpotential of 59.0mV at 10mAcm-2. Operando Raman and first principles calculations reveal that the interfacial water to the PHCo sites and the accelerated proton transfer are conducive to the adsorption and dissociation of H2O molecules. Meanwhile, the upshifted d-band center of PHCo optimizes the adsorption/desorption of H*. This work provides a unique synthesis of hollow Co nanoshells via the Kirkendall effect and insights to water dissociation on catalyst surfaces with tailored charge states.

Theoretical insights into enantioselective [2 + 1] cyclopropanation reactions of diazo compounds with electron-deficient olefins.

The cyclopropane skeleton plays a significant role in bioactive molecules due to its distinctive structural properties. This has sparked keen interest and in-depth exploration in the field of stereoselective synthesis of cyclopropane derivatives. In the present study, the mechanism and the origin of stereoselectivity of diastereodivergent synthesis of cyclopropane derivatives via the catalyst-free [2 + 1]-cyclopropanation reactions of 3-diazo-N-methylindole (R1) with two types of electron-deficient olefins (R2 and R3) in both aqueous and toluene media have been studied using the DFT calculations. The findings indicate that these [2 + 1] cycloaddition reactions proceed in two stages, where the first step is not only the rate-determining step but also critically dictates the stereoselectivity of the product. The calculated diastereomeric ratios are in agreement with the experimental results. Furthermore, by utilizing non-covalent interaction (NCI) analysis and energy decomposition analysis based on molecular force fields (EDA-FF), we elucidated that the electrostatic interactions between reactant fragments in the transition state TS1s for the first step are the predominant factors determining the stereoselectivity, as opposed to the experimentally hypothesized steric hindrance and π-π stacking interactions. The geometrical structures of all minima and transition states on the potential energy surface (PES) in solvents water and toluene were fully optimized using the DFT method at the M06-2X(D3)/SMD/6-31 + G(d,p) level of theory. Single-point energy calculations were carried out based on the optimized geometries in the solution at the M06-2X(D3)/6-311 + G(d,p) level. All the DFT calculations were performed using the Gaussian 09 software. The optimized molecular structures were visualized using CYLview software. NCI analysis was performed using the Multiwfn and VMD softwares. The Multiwfn program was also used for CDFT and EDA-FF analyses.

Strain-induced enhancement of surface self-diffusion on strontium titanate (001) surfaces.

We present a numerical investigation of self-diffusion on strontium titanate TiO2-terminated (001) surfaces via density functional theory. Our calculations first indicate that Ti has the highest diffusion barrier with approximately 2.20 eV, thus representing the rate-limiting step for surface self-diffusion. Furthermore, the higher energy barriers of O and Ti in comparison to O2and TiO2indicate electronic activity with the surface atoms. Under the consideration of equi-biaxial strain as it would be encountered in e.g. heteroepitaxial thin films, the diffusion barriers for surface self-diffusion decrease for both compressive and tensile strains between -6% and 2%. For larger strains, we observe plastic deformations. This possibility to lower the energy barrier paves the way for accelerated and possible new mechanisms of surface diffusion and reconstruction of strontium titanate structures in a wide range of applications.

Efficient net transfer-dehydrogenation of glycerol: NNN pincer-Mn and manganese chloride as a catalyst unlocks the effortless production of lactic acid and isopropanol.

Herein, a series of pincer-Mn complexes based on bis(imino)pyridine ligands of the type R2NNN (R = tBu, iPr, Cy and Ph) were synthesized and characterized using various spectroscopic techniques. SCXRD studies revealed a trigonal bipyramidal geometry around the metal center in all the complexes. EPR spectroscopy confirmed the presence of high-spin Mn(II) centers with the consistent observation of sextets in EPR spectra. Additionally, solution magnetic moment measurement exhibited values ranging from 5.8 to 6.2 BM for all the complexes, which are in accordance with the theoretical value of 5.92 BM. HRMS analysis complemented structural characterization, showing fragments corresponding to various solvent adducts and derivatives of the complexes. Subsequently, the synthesized complexes were investigated for their catalytic activity in the transfer dehydrogenation of glycerol to lactic acid in the presence of acetone. Among the considered complexes, the catalyst Ph2NNNMnCl2 was found to be highly efficient. Remarkably, a yield of 92% LA was observed with >99% selectivity at 0.5 mol% loading of Ph2NNNMnCl2 in the presence of 1 equivalent of NaOH at 140 °C in 24 h, surpassing the yield obtained from its precursor MnCl2·4H2O, where a yield of 72% LA was observed with 96% selectivity under similar reaction conditions. This catalytic system was further investigated with a range of acceptors, and good to moderate yields were observed in most cases. Moreover, several control experiments, including reaction with PPh3, CS2 and Hg, highlighted the major involvement of molecular species in the reaction medium. Deuterium labelling studies indicated the involvement of C-H bond activation in the catalytic cycle but not in the rate-determining step (RDS), with a secondary kinetic isotope effect (KIE) of 1.25.

Mechanistic Implications of the Varying Susceptibility of PAHs to Pyro-Catalytic Treatment as a Function of Their Ionization Potential and Hydrophobicity.

Transition metal catalysts in soil constituents (e.g., clays) can significantly decrease the pyrolytic treatment temperature and energy requirements for efficient removal of polycyclic aromatic hydrocarbons (PAHs) and, thus, lead to more sustainable remediation of contaminated soils. However, the catalytic mechanism and its rate-limiting steps are not fully understood. Here, we show that PAHs with lower ionization potential (IP) are more easily removed by pyro-catalytic treatment when deposited onto Fe-enriched bentonite (1.8% wt. ion-exchanged content). We used four PAHs with decreasing IP: naphthalene > pyrene > benz(a)anthracene > benzo(g,h,i)perylene. Density functional theory (DFT) calculations showed that lower IP results in stronger PAH adsorption to Fe(III) sites and easier transfer of π-bond electrons from the aromatic ring to Fe(III) at the onset of pyrolysis. We postulate that the formation of aromatic radicals via this direct electron transfer (DET) mechanism is the initiation step of a cascade of aromatic polymerization reactions that eventually convert PAHs to a non-toxic and fertility-preserving char, as we demonstrated earlier. However, IP is inversely correlated with PAH hydrophobicity (log Kow), which may limit access to the Fe(III) catalytic sites (and thus DET) if it increases PAH sorption to soil OM. Thus, ensuring adequate contact between sorbed PAHs and the catalytic reaction centers represents an engineering challenge to achieve faster remediation with a lower carbon footprint via pyro-catalytic treatment.

The two alternative NADH:quinone oxidoreductases from Staphylococcus aureus: two players with different molecular and cellular roles.

Staphylococcus aureus is an opportunistic pathogen that has emerged as a major public health threat due to the increased incidence of its drug resistance. S. aureus presents a remarkable capacity to adapt to different niches due to the plasticity of its energy metabolism. In this work, we investigated the energy metabolism of S. aureus, focusing on the alternative NADH:quinone oxidoreductases, NDH-2s. S. aureus presents two genes encoding NDH-2s (NDH-2A and NDH-2B) and lacks genes coding for Complex I, the canonical respiratory NADH:quinone oxidoreductase. This observation makes the action of NDH-2s crucial for the regeneration of NAD+ and, consequently, for the progression of metabolism. Our study involved the comprehensive biochemical characterization of NDH-2B and the exploration of the cellular roles of NDH-2A and NDH-2B, utilizing knockout mutants (Δndh-2a and Δndh-2b). We show that NDH-2B uses NADPH instead of NADH, does not establish a charge-transfer complex in the presence of NADPH, and its reduction by this substrate is the catalytic rate-limiting step. In the case of NDH-2B, the reduction of the flavin is inherently slow, and we suggest the establishment of a charge transfer complex between NADP+ and FADH2, as previously observed for NDH-2A, to slow down quinone reduction and, consequently, prevent the overproduction of reactive oxygen species, which is potentially unnecessary. Furthermore, we observed that the lack of NDH-2A or NDH-2B impacts cell growth, volume, and division differently. The absence of these enzymes results in distinct metabolic phenotypes, emphasizing the unique cellular roles of each NDH-2 in energy metabolism.IMPORTANCEStaphylococcus aureus is an opportunistic pathogen, posing a global challenge in clinical medicine due to the increased incidence of its drug resistance. For this reason, it is essential to explore and understand the mechanisms behind its resistance, as well as the fundamental biological features such as energy metabolism and the respective players that allow S. aureus to live and survive. Despite its prominence as a pathogen, the energy metabolism of S. aureus remains underexplored, with its respiratory enzymes often escaping thorough investigation. S. aureus bioenergetic plasticity is illustrated by its ability to use different respiratory enzymes, two of which are investigated in the present study. Understanding the metabolic adaptation strategies of S. aureus to bioenergetic challenges may pave the way for the design of therapeutic approaches that interfere with the ability of the pathogen to successfully adapt when it invades different niches within its host.

Coacervation in Slow Motion: Kinetics of Complex Micelle Formation Induced by the Hydrolysis of an Antibiotic Prodrug.

Colistin methanesulfonate (CMS) is the less-toxic prodrug of highly nephrotoxic colistin. To develop and understand highly necessary new antibiotic formulations, the hydrolysis of CMS to colistin must be better understood. Herein, with the addition of poly(ethylene oxide)-b-poly(methacrylic acid) (PEO-b-PMAA) to CMS, we show that we can follow the hydrolysis kinetics, employing small-angle X-ray scattering (SAXS) through complex coacervation. During this hydrolysis, hydroxy methanesulfonate (HMS) groups from CMS are cleaved, while the newly formed cationic amino groups complex with the anionic charge from the PMAA block. As the hydrolysis of HMS groups is slow, we can follow the complex coacervation process by the gradual formation of complex micelles containing activated antibiotics. Combining mass spectrometry (MS) with SAXS, we quantify the hydrolysis as a function of pH. Upon modeling the kinetic pathways, we found that complexation only happens after complete hydrolysis into colistin and that the process is accelerated under acidic conditions. At pH = 5.0, effective charge switching was identified as the slowest step in the CMS conversion, constituting the rate-limiting step in colistin formation.

Structure characteristics and combustion kinetics of the co-pyrolytic char of rice straw and coal gangue

Co-combustion is a technology that enables the simultaneous and efficient utilization of biomass and coal gangue (CG). Nevertheless, the factors that affect the combustibility of co-pyrolytic char, which represents the rate-determining step of the entire co-combustion process, remain unclear. This study investigates the impact of the physicochemical properties of co-pyrolytic char, including pore structure, carbon structure, and alkali metals, on the combustion characteristics. The TGA analysis indicates that the ignition and burnout temperatures of the co-pyrolytic char increase as the CG mixing ratio increases, resulting in a prolonged combustion. This is due to the fact that the carbon structure of the co-pyrolytic char becomes increasingly aromatic, accompanied by a reduction in aliphatic hydrocarbons and oxygen-containing groups as the CG mixing ratio increases. Furthermore, the high ash content of the CG is another significant factor contributing to the observed reduction in combustibility. The reaction between mullite, quartz in CG, and alkali metals in biomass results in the formation of aluminosilicate, which reduces the catalytic ability of alkali metals. Furthermore, the char combustion kinetics are analyzed by the KAS method, and the results indicate that the introduction of CG increases the activation energy of the entire char combustion process. The activation energy of the 80RS20CG is within the range of 102.22–164.99 kJ/mol, while the RS char is within the range of 89.87–144.67 kJ/mol.

Mechanistic Insights into the Direct Deoxygenation of Phenolic Compounds over Novel Heusler Alloy Catalysts.

The catalytic deoxygenation of phenolic compounds is a crucial step in the valorization of biomass resources, which can effectively enhance the heating value and stability of primary biofuel. In this study, the catalytic mechanism of four Heusler alloy catalysts for the direct deoxidation pathway of phenol was studied through electronic structure regulation by element occupation. We found that Heusler alloys catalysts exhibit excellent catalytic activity in the dissociation activation of H2 and the cleavage of aryl hydroxyl bond (CAr-OH) bonds. The energy barriers for the direct cleavage of the CAr-OH bond in phenol on Ni2MoAl, Co2MoAl, Ni2NbAl and Ni2MoGa catalysts are 0.86, 0.95, 1.09, and 1.28 eV, respectively. And Y element of the X2YZ catalyst has a significant impact on this reaction, while the X element has a complex influence on the hydrogenation step of the unsaturated benzene ring. Microkinetic analysis further substantiates that the phenol (CAr-OH) bond cleavage step in the reaction exhibits a fast reaction rate and high extent of reaction. The reaction of hydroxyl hydrogenation to produce water exhibits the highest energy barrier, serving as the rate-determining step of the entire reaction. This issue could potentially be addressed by further fine-tuning the electronic structure.

5-aminolevulinic acid induced photodynamic reactions in diagnosis and therapy for female lower genital tract diseases

Since the patients suffering from female lower genital tract diseases are getting younger and younger and the human papilloma virus (HPV) infection is becoming more widespread, the novel non-invasive precise modalities of diagnosis and therapy are required to remain structures of the organ and tissue, and fertility as well, by which the less damage to normal tissue and fewer adverse effects are able to be achieved. In all nucleated mammalian cells, 5-Aminolevulinic acid (5-ALA) is an amino acid that occurs spontaneously, which further synthesizes in the heme biosynthetic pathway into protoporphyrin IX (PpIX) as a porphyrin precursor and photosensitizing agent. Exogenous 5-ALA avoids the rate-limiting step in the process, causing PpIX buildup in tumor tissues. This tumor-selective PpIX distribution after 5-ALA application has been used successfully for tumor photodynamic diagnosis (PDD) and photodynamic therapy (PDT). Several ALA-based drugs have been used for ALA-PDD and ALA-PDT in treating many (pre)cancerous diseases, including the female lower genital tract diseases, yet the ALA-induced fluorescent theranostics is needed to be explored further. In this paper, we are going to review the studies of the mechanisms and applications mainly on ALA-mediated photodynamic reactions and its effectiveness in treating female lower genital tract diseases.

N-Vacancy Enriched Porous BN Fibers for Enhanced Polysulfides Adsorption and Conversion in High-Performance Lithium-Sulfur Batteries.

Severe shuttle effect of soluble polysulfides and sluggish redox kinetics have been thought of as the critical issues hindering the extensive applications of lithium-sulfur batteries (LSBs). Herein, one-dimensional boron nitride (1D BN) fibers with abundant pores and sufficient N-vacancy defects were synthesized using a thermal crystallization following a pre-condensation step. The 1D structure of BN facilitates unblocked ions diffusion pathways during charge/discharge cycles. The embedded pores within the polar BN strengthen the immobilization of polysulfides via both physical confinement and chemical interaction. Moreover, the highly exposed active surface area and intentionally created N-vacancy sites substantially promote reaction kinetics by lowering the energy barriers of the rate-limiting steps. After incorporating with conductive carbon networks and elemental S, the as-prepared S/Nv-BN@CBC cathode of LSBs deliver an initial discharge capacity of up to 1347 mAh g-1 at 200 mA g-1, while maintaining a low decay rate of 0.03% per cycle over 1000 cycles at 1600 mA g-1. This work offers an effective strategy to mitigate the shuttle effect and highlights the significant potential of defect-engineered BN in accelerating the reaction kinetics of LSBs.

Enhanced electrocatalytic biomass oxidation at low voltage by Ni2+-O-Pd interfaces

Challenges in direct catalytic oxidation of biomass-derived aldehyde and alcohol into acid with high activity and selectivity hinder the widespread biomass application. Herein, we demonstrate that a Pd/Ni(OH)2 catalyst with abundant Ni2+-O-Pd interfaces allows electrooxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid with a selectivity near 100 % and 2, 5-furandicarboxylic acid yield of 97.3% at 0.6 volts (versus a reversible hydrogen electrode) in 1 M KOH electrolyte under ambient conditions. The rate-determining step of the intermediate oxidation of 5-hydroxymethyl-2-furancarboxylic acid is promoted by the increased OH species and low C–H activation energy barrier at Ni2+-O-Pd interfaces. Further, the Ni2+-O-Pd interfaces prevent the agglomeration of Pd nanoparticles during the reaction, greatly improving the stability of the catalyst. In this work, Pd/Ni(OH)2 catalyst can achieve 100% 5-hydroxymethylfurfural conversion and >90% 2, 5-furandicarboxylic acid selectivity in a flow-cell and work stably over 200 h under a fixed cell voltage of 0.85 V.

A Mechanistic Insight into the Acidic-stable MnSb2O6 for Electrocatalytic Water Oxidation.

The abundant, active, and acidic-stable catalysts for the oxygen evolution reaction (OER) are rare to the proton exchange membrane-based water electrolysis. Mn-based materials show promise as electrocatalysts for OER in acid electrolytes. However, the relationship between the stability, activity and structure of Mn-based catalysts in acidic environments remains unclear. In this study, phase-pure MnSb2O6 was successfully prepared and investigated as a catalyst for OER in a sulfuric acid solution (pH of 2.0). A comprehensive mechanistic comparison between MnSb2O6 and Mn3O4 revealed that the rate-determining step for OER on MnSb2O6 is the direct formation of MnIV=O from MnII-H2O by the 2H+/2e- process. This process avoids the rearrangement of adjacent MnIII intermediates, leading to outstanding stability and activity.

Autosomal Recessive Guanosine Triphosphate Cyclohydrolase I Deficiency: Redefining the Phenotypic Spectrum and Outcomes.

The GCH1 gene encodes the enzyme guanosine triphosphate cyclohydrolase I (GTPCH), which catalyzes the rate-limiting step in the biosynthesis of tetrahydrobiopterin (BH4), a critical cofactor in the production of monoamine neurotransmitters. Autosomal dominant GTPCH (adGTPCH) deficiencyis the most common cause of dopa-responsive dystonia (DRD), whereas the recessive form (arGTPCH) is an ultrarare and poorly characterized disorder with earlier and more complex presentation that may disrupt neurodevelopmental processes. Here, we delineated the phenotypic spectrum of ARGTPCHD and investigated the predictive value of biochemical and genetic correlates for disease outcome. The aim was to study 4 new cases of arGTPCH deficiency and systematically review patients reported in the literature. Clinical, biochemical, and genetic data and treatment response of 45 patients are presented. Three phenotypes were outlined: (1) early-infantile encephalopathic phenotype with profound disability (24 of 45 patients), (2) dystonia-parkinsonism phenotype with infantile/early-childhood onset of developmental stagnation/regression preceding the emergence of movement disorder (7 of 45), and (3) late-onset DRD phenotype (14 of 45). All 3 phenotypes were responsive to pharmacological treatment, which for the first 2 must be initiated early to prevent disabling neurodevelopmental outcomes. A gradient of BH4 defect and genetic variant severity characterizes the 3 clinical subgroups. Hyperphenylalaninemia was not observed in the second and third groups and was associated with a higher likelihood of intellectual disability. The clinical spectrum of arGTPCH deficiency is a continuum from early-onset encephalopathies to classical DRD. Genotype and biochemical alterations may allow early diagnosis and predict clinical severity. Early treatment remains critical, especially for the most severe patients.

Potential of V-Si72, V-C72, and V-Al36N36 as catalysts for oxygen reduction reaction.

The capacities of V-Si72, V-C72, and V-Al36N36 nanocages to catalyze the ORR processes have been investigated. The acceptable pathways of ORR processes on V-Si72, V-C72, and V-Al36N36 nanocages have been examined by DSD-PBEPBE-D3/aug-cc-pVDZ, PW91PW91/aug-cc-pVDZ, and COSMO model in the gas phase and water. The ΔGreaction values of reaction steps of ORR pathways on V-Si72, V-C72, and V-Al36N36 nanocages are calculated. The Eadoption and Eformation of V-Si72, V-C72, and V-Al36N36 nanocages are negative values and these nanostructures are stable materials. The H2O has the lowest Eadsorption on V-Si72, V-C72, and V-Al36N36 nanocages. The *OH formation, creation of *OH-OH*, and formation of O* are rate-determining steps of ORR mechanisms. The overpotential values of ORR processes on V-Si72, V-C72, and V-Al36N36 nanocages are 0.41, 0.37, and 0.30V, respectively. The V-Al36N36 nanocage have lower overpotential for ORR processes than V-Si72 and V-C72 nanocages by DSD-PBEPBE-D3/aug-cc-pVDZ, PW91PW91/aug-cc-pVDZ, and COSMO model in the gas phase and water. The V-Al36N36 nanocage have more negative ∆Greaction for reaction steps of ORR than V-Si72 and V-C72 nanocages. The V-Al36N36 nanocage with lower overpotential is proposed as an effective catalyst for ORR processes via studied pathways. The DSD-PBEPBE-D3/aug-cc-pVDZ method has been used to optimize and calculate the frequencies of V-Si72, V-C72, and V-Al36N36 nanocages in GAMESS software. The complexes of O, OH, OOH, and H2O with V-Si72, V-C72, and V-Al36N36 nanocages are optimized and frequencies are determined by the DSD-PBEPBE-D3/aug-cc-pVDZ method. The Gactivation and ∆Greaction of ORR pathways on V-Si72, V-C72, and V-Al36N36 nanocages are calculated by DSD-PBEPBE-D3/aug-cc-pVDZ, PW91PW91/aug-cc-pVDZ, and COSMO model in the gas phase and water.

Mechanism insight into the conversion between COS and thiophene during CO2 gasification of carbon-based fuels

Thiophene is the organic sulfur with good thermal stability in carbon-based fuel, clarifying the conversion mechanism between thiophene and COS is beneficial for achieving in-situ sulfur fixation during CO2 gasification of carbon-based fuels, but the mechanism has rarely been reported. Therefore, calculations based on density functional theory were performed and 16 reaction paths were proposed in this research, clarifying the decomposition mechanism of thiophene and re-fixation mechanism of COS. The attachment of CO2 will lead to the destruction of the thiophene ring and the generation of COS, and CO2 adsorption is the rate-determined step, while the carbon atom that adjacent sulfur atom is the reaction active site. However, the energy barriers of CO2 addition reactions are lower than those of CO2 adsorption reactions, and the energy barrier of reactions occurring on the aliphatics are lower than that occurring on the aromatics. The combination of CO2 and thiophene will thermodynamically lead to the generation of COS and CO. Moreover, gaseous sulfur generated from thiophene decomposition will be converted mutually, while H2S will not be converted into COS. Furthermore, COS will be captured by char, forming solid organic sulfur. The re-fixation of COS will occur on aliphatic chains from the decomposition of aromatics.

Comparative Studies on Full Dehydrogenation of Dodecahydro-N-Ethylcarbazole on Pd(111) and Ni(111) Surfaces: Mechanism and Catalytic Enhancement.

Dodecahydro-N-ethylcarbazole (12H-NEC) is regarded as the most promising liquid organic hydrogen carrier for hydrogen storage and transportation. Understanding the mechanism of 12H-NEC dehydrogenation and developing cost-effective catalysts are significant. Pd is a high-performance catalyst for 12H-NEC but is not cost-effective, and Ni is just the opposite. How to understand the whole process of full dehydrogenation and improve the performance of Ni become two key questions. Herein, we systematically investigated the mechanism of the full dehydrogenation of 12H-NEC on Pd(111) and Ni(111) for the first time. By calculating all the barriers in the whole dehydrogenation process, we identified that 3H-NEC to 2H-NEC is the rate-determining step and Ni is catalytically less effective than Pd, which is attributed to its narrower d-band distribution and a 0.32 eV higher d-band center than that of Pd. To improve the performance of Ni, we further introduced dopants of Au, Ag, Cu, Pd, Pt, Ru, Rh, Zn, and Al. We found that Ag doping brings a downshift of the d-band center from -1.29 to -1.67 eV and reduces the barrier of 4H-NEC to NEC from 0.94 to 0.76 eV. This study provides new insights into the catalytic mechanism and performance-tuning strategy to help future experimental synthesis.

Comparative Studies on Full Dehydrogenation of Dodecahydro-N-Ethylcarbazole on Pd(111) and Ni(111) Surfaces: Mechanism and Catalytic Enhancement.

Dodecahydro-N-ethylcarbazole (12H-NEC) is regarded as the most promising liquid organic hydrogen carrier for hydrogen storage and transportation. Understanding the mechanism of 12H-NEC dehydrogenation and developing cost-effective catalysts are significant. Pd is a high-performance catalyst for 12H-NEC but is not cost-effective, and Ni is just the opposite. How to understand the whole process of full dehydrogenation and improve the performance of Ni become two key questions. Herein, we systematically investigated the mechanism of the full dehydrogenation of 12H-NEC on Pd(111) and Ni(111) for the first time. By calculating all the barriers in the whole dehydrogenation process, we identified that 3H-NEC to 2H-NEC is the rate-determining step and Ni is catalytically less effective than Pd, which is attributed to its narrower d-band distribution and a 0.32 eV higher d-band center than that of Pd. To improve the performance of Ni, we further introduced dopants of Au, Ag, Cu, Pd, Pt, Ru, Rh, Zn, and Al. We found that Ag doping brings a downshift of the d-band center from -1.29 to -1.67 eV and reduces the barrier of 4H-NEC to NEC from 0.94 to 0.76 eV. This study provides new insights into the catalytic mechanism and performance-tuning strategy to help future experimental synthesis.

Interface Engineering of the Cu1.5Mn1.5O4/CeO2 Heterostructure for Highly Efficient Electrocatalytic Nitrate Reduction to Ammonia.

The electrochemical nitrate reduction reaction (NO3RR) is considered a sustainable technology to convert the nitrate pollutants to ammonia. However, developing highly efficient electrocatalysts is necessary and challenging given the slow kinetics of the NO3RR with an eight-electron transfer process. Here, a Cu1.5Mn1.5O4 (CMO)/CeO2 heterostructure with rich interfaces is designed and fabricated through an electrospinning and postprocessing technique. Benefiting from the strong coupling between CMO and CeO2, the optimized CMO/CeO2-2 catalyst presents excellent NO3RR performance, with NH3 Faraday efficiency (FE) up to 93.07 ± 1.45% at -0.481 V vs reversible hydrogen electrode (RHE) and NH3 yield rate up to 48.06 ± 1.32 mg cm-2 h-1 at -0.681 V vs RHE. Theoretical calculations demonstrate that the integration of CeO2 with CMO modulates the adsorption/desorption process of the reactants and intermediates, showing a reduced energy barrier in the rate determination step of NO* to N* and achieving an outstanding NO3RR performance.

Hydrophobic Microenvironment Modulation of Ru Nanoparticles in Metal-Organic Frameworks for Enhanced Electrocatalytic N2 Reduction.

The modulation of the chemical microenvironment surrounding metal nanoparticles (NPs) is an effective means to enhance the selectivity and activity of catalytic reactions. Herein, a post-synthetic modification strategy is developed to modulate the hydrophobic microenvironment of Ru nanoparticles encapsulated in a metal-organic framework (MOF), MIP-206, namely Ru@MIP-Fx (where x represents perfluoroalkyl chain lengths of 3, 5, 7, 11, and 15), in order to systematically explore the effect of the hydrophobic microenvironment on the electrocatalytic activity. The increase of perfluoroalkyl chain length can gradually enhance the hydrophobicity of the catalyst, which effectively suppresses the competitive hydrogen evolution reaction (HER). Moreover, the electrocatalytic production rate of ammonia and the corresponding Faraday efficiency display a volcano-like pattern with increasing hydrophobicity, with Ru@MIP-F7 showing the highest activity. Theoretical calculations and experiments jointly show that modification of perfluoroalkyl chains of different lengths on MIP-206 modulates the electronic state of Ru nanoparticles and reduces the rate-determining step for the formation of the key intermediate of N2H2 *, leading to superior electrocatalytic performance.