High Barrier Research Articles

Entanglement of Coupled Harmonic Oscillators without and with Tunneling Effect and Correction Factor

Seeing its simplicity of processing, the system of two coupled harmonic oscillators have witnessed a quick growth of research conducted to quantum information. This approach is explicitly investigated in this paper, in particularly entanglement concept is proved to be intimately related to the tunneling effect. We examine analytically entanglement dynamics by introducing the Lewis and Riesenfeld invariant operator in the Heisenberg picture approach to compute the density matrix on the based of an exact treatment. We use Wigner function of the mixed state as an essential tool to move to linear entanglement entropies and we compute the corresponding correction factor. We follow numerically the evolution of entanglement dynamics without and under tunneling through the quantum potential barrier by introducing two particular models between simple and damped coupled harmonic oscillators. Entanglement dynamics is considered to be average without tunneling, it grows upon encountering the potential barrier and remains moderately constant inside barrier. This specificity is extended for both models but with higher values for damped coupled harmonic oscillators consequently the damping effect rapidly increases entanglement. Correction factor is also considered for both models, it show that; low temperature and high potential barriers make the system more disruptive. An increase of the coupling parameter of the system increase correction factor. Damping make the correction factor more important so damping disturbs more the system. Interference effect increase correction factor and it shows an interference between the values of the barrier penetration integral.

DFT Study on Copper‐Catalyzed Hydroboration of 1,3‐Diynes: Mechanism, Selectivity, and Comparison with Ruthenium

Density functional theory calculations have been performed to explore the mechanism of copper‐catalyzed hydroboration of 1,3‐diyne with HBpin. The catalytic cycles are composed of three elementary processes in succession, namely, the generation of copper hydride species, migratory insertion and σ‐bond metathesis, among which the σ‐bond metathesis step is rate‐determining with a free‐energy barrier of 19.7 kcal/mol. The syn‐addition selectivity originates from the high barrier for converting (Z)‐product to (E)‐product. Effects of diphosphine ligands and substituents on the reactivity were also addressed. Lastly, this copper‐catalyzed hydroboration was compared with a related ruthenium‐catalyzed one, and the obtained results indicated that copper‐catalyzed hydroboration has a more favorable σ‐bond metathesis step but more challenging migratory insertion step as compared to the ruthenium‐catalyzed counterpart. Wavefunction analyses were performed to understand the observed behaviors.

Toward mechanical recyclability of high barrier food packaging films through filler incorporation on the EVOH layer

AbstractTo preserve food from moisture and oxygen, polymers, such as ethylene vinyl alcohol (EVOH) are used in multilayer structures to provide oxygen barrier, while low‐density polyethylene (LDPE) is used for a water vapor barrier. While this material combination is functionally ideal, it may not comply with the new packaging recycling guidelines. Some European markets have implemented rules that limit the weight percentage of EVOH in LDPE films. One way to increase recyclability is by reducing the amount of EVOH in the film structure while maintaining the packaging's oxygen barrier properties. To achieve this, it is necessary to improve the barrier properties of EVOH. With this objective in mind, this study evaluated the incorporation of nanoclays (NC), cellulose microcrystals (MCC), silicon dioxide nanoparticles (SiO2), and cellulose nanocrystals (CNC) into an EVOH matrix. The results indicate that NC and MCC facilitate a stable blown film extrusion process and have a better dispersion in the EVOH matrix. Based on this finding, three‐layer films (with an ABA configuration) consisting of LDPE (A) and EVOH (7 μm layer) with 0.5 or 1 wt.% MCC or NC (B) were produced to protect the EVOH from moisture and enable blown film processing. The oxygen transmission rate (OTR) values were lowest for 0.5 wt.% NC and 1 wt.% MCC incorporation. Although the films with micro and nanoparticles had increased haze, this did not affect the visibility of the packaged food.

A novel approach to the cause of death identification—multi-strategy integration of multi-organ FTIR spectroscopy information using machine learning

Identifying the cause of death has always been a major focus and challenge in forensic practice and research. Traditional techniques for determining the causes of death are time-consuming, labor-intensive, have high professional barriers, and are vulnerable to significant subjective bias. Additionally, most current studies on causes of death are limited to specific organs and single causes. To overcome these challenges, this study utilized simple and rapid fourier transform infrared spectroscopy (FTIR) detection technology, integrating data from six organs—heart, liver, spleen, lung, kidney, and brain. The optimum model for identifying seven different causes of death was determined by evaluating the performance of models developed using the model efficiencies of single-organ (SO), single-organ model fusion (SOMF), multi-organ data fusion (MODF), and multi-organ data model fusion (MODMF) modeling methods. Considering factors such as operational costs, model performance, and model complexity, the MODF artificial neural network (ANN) model was found to be the most suitable choice for constructing a cause of death identification model, with a cross-validation mean accuracy of 0.960 and a test set accuracy of 0.952. The heart and kidney contributed more spectral features to the construction of the cause of death identification model compared to other organs. This study not only demonstrated that data fusion and model fusion are effective strategies for improving model performance but also provided a comprehensive data analysis framework and process for modeling with small sample multi-modal data (multiple organ data). In conclusion, by exploring various approaches, this study offers new solutions for identifying the cause of death.

Strontium Doped IrOx Triggers Direct O-O Coupling to Boost Acid Water Oxidation Electrocatalysis.

The discovery of efficient and stable electrocatalysts for the oxygen evolution reaction (OER) in acidic conditions is crucial for the commercialization of proton-exchange membrane water electrolyzers. In this work, we propose a Sr(OH)2-assisted method to fabricate a (200) facet highly exposed strontium-doped IrOx catalyst to provide available adjacent iridium sites with lower Ir-O covalency. This design facilitates direct O-O coupling during the acidic water oxidation process, thereby circumventing the high energy barrier associated with the generation of *OOH intermediates. Benefiting from this advantage, the resulting Sr-IrOx catalyst exhibits an impressive overpotential of 207 mV at a current density of 10 mA cm-2 in 0.5 M H2SO4. Furthermore, a PEMWE device utilizing Sr-IrOx as the anodic catalyst demonstrates a cell voltage of 1.72 V at 1 A cm-2 and maintains excellent stability for over 500 hours. Our work not only provides guidance for the design of improved acidic OER catalysts but also encourages the development of iridium-based electrocatalysts with novel mechanisms for other electrocatalytic reactions.

Exploration of phytoconstituents of Medhya Rasayana herbs to identify potential inhibitors for cerebroside sulfotransferase through high-throughput screening.

Cerebroside sulfotransferase (CST) is a key enzyme in sulfatide biosynthesis and regulation of the myelin sheath in the nervous system. To counter sulfatide accumulation with the deficiency of aryl sulfatase A, CST is considered a target protein in substrate reduction therapy in metachromatic leukodystrophy. In this study, 461 phytoconstituents from four herbs of Medhya Rasayana were screened using multi-pronged virtual screening methods including molecular docking, molecular dynamics (MD) simulation, and reverse pharmacophore analysis. The initial screening of the top 15 hits was based on the binding affinity of the compounds toward the CST substrate-binding site using the lowest free energy of a binding score cutoff of ≤ -7.5 kcal/mol, with the number of conformations in the largest cluster more than 75. The absorption, distribution, metabolism, and excretion (ADME) and toxicity-based pharmacokinetic analysis delivered the top four hits: 18alpha-glycyrrhetinic acid, lupeol, alpha carotene, and beta-carotene, with high blood-brain barrier permeability and negligible toxicity. Furthermore, a 100-ns simulation of protein-ligand complexes with a trajectory analysis of structural deviation, compactness, intramolecular interactions, principal component analysis, free energy landscape, and dynamic cross-correlation analysis showed the binding potential and positioning of the four hits in the binding pocket. Thus, an in-depth analysis of protein-ligand interactions from pre- and post-molecular dynamics simulation, along with reverse pharmacophore mapping, suggests that 18alpha-glycyrrhetinic acid is the most potent and specific CST inhibitor, while beta-carotene could be considered the second most potent compound for CST inhibition as it also exhibited overall stability throughout the simulation. Therefore, the computational drug screening approach applied in this study may contribute to the development of oral drugs as a therapeutic option for metachromatic leukodystrophy.

P-Block Aluminum Single-Atom Catalyst for Electrocatalytic CO2 Reduction with High Intrinsic Activity.

Atomically dispersed transition metal sites on nitrogen-doped carbon catalysts hold great potential for the electrochemical CO2 reduction reaction (CO2RR) to CO due to their encouraging selectivity. However, their intrinsic activity is restricted by the hurdle of the high energy barrier of either *COOH formation or *CO desorption due to the scaling relationship. Herein, we discover a p-block aluminum single-atom catalyst (Al-NC) featuring an Al-N4 site that enables disentangling this hurdle, which endows a moderate reaction kinetic barrier for *COOH formation and *CO desorption, as validated by in situ attenuated total reflection infrared spectroscopy and theoretical simulations. As a result, the developed Al-NC shows a CO Faradaic efficiency (FECO) of up to 98.76% at -0.65 V vs RHE and an intrinsic catalytic turnover frequency of 3.60 s-1 at -0.99 V vs RHE, exceeding those of the state-of-the-art Ni-NC and Fe-NC counterparts. Moreover, it also delivers a partial CO current of 309 mA·cm-2 at 93.65% FECO and 605 mA at >85% FECO in a flow cell and membrane electrode assembly (MEA), respectively. Strikingly, when using low-concentration CO2 (30%) as the feedstock, this catalyst can still deliver a partial CO current of 240 mA at >80% FECO in the MEA. Considering the earth-abundant character of the Al element and the high intrinsic activity of the Al-NC catalyst, it is a promising alternative to today's transition metal-based single-atom catalysts.

Boron-Doping Engineering in AgCd Bimetallic Catalyst Enabling Efficient CO2 Electroreduction to CO and Aqueous Zn-CO2 Batteries.

The limited adsorption and activation of CO2 on catalyst and the high energy barrier for intermediate formation hinder the development of electrochemical CO2 reduction reactions (CO2RR). Herein, this work reports a boron (B) doping engineering in AgCd bimetals to alleviate the above limitations for efficient CO2 electroreduction to CO and aqueous Zn-CO2 batteries. Specifically, the B-doped AgCd bimetallic catalyst (AgCd-B) is prepared via a simple reduction reaction at room temperature. A combination of in situ experiments and density functional theory (DFT) calculations demonstrates that B-doping simultaneously enhances the adsorption and activation of CO2 and reduces the binding energy of the intermediates by moderating the electronic structure of bimetals. As a result, the AgCd-B catalyst exhibits a high CO Faraday efficiency (FECO) of 99% at -0.8V versus reversible hydrogen electrode (RHE). Additionally, it maintains a FECO over 92% at a wide potential window of 600mV (-0.6 to -1.1V versus RHE). Furthermore, the AgCd-B catalyst coupled with the Zn anode to assemble aqueous Zn-CO2 batteries shows a power density of 20.18mW cm-2 and a recharge time of 33h.

Low-temperature oxidation of methane mediated by Al-doped ZnO cluster and nanowire: a first-principles investigation.

First-principles calculations are performed to investigate the catalytic oxidation of methane by using N2O as an oxidizing agent over aluminum (Al)-doped Zn12O12 cluster and (Zn12O12)2 nanowire. The impact of Al impurity on the geometry, electronic structure, and surface reactivity of Zn12O12 and (Zn12O12)2 is thoroughly studied. Our study demonstrates that Al-doped ZnO systems have a better adsorption ability than the corresponding pristine counterparts. It is found that N2O molecule is initially decomposed on the Al site to provide the N2 molecule, and an Al-O intermediate which is an active species for the CH4 oxidation. The conversion of CH4 into CH3OH over AlZn11O12 and (AlZn11O12)2 requires an activation energy of 0.45 and 0.29eV, respectively, indicating it can be easily performed at normal temperatures. Besides, the overoxidation of methanol into formaldehyde cannot take place over the AlZn11O12 and (AlZn11O12)2, due to the high energy barrier needed to dissociate C-H bond of the CH3O intermediate. Dispersion-corrected density functional theory calculations were performed through GGA-PBE exchange-correlation functional combined with a numerical double-ζ plus polarization (DNP) basis set as implemented in DMol3. To include the relativistic effects of core electrons of Zn atoms, DFT-semicore pseudopotentials were adopted. The DFT + D scheme proposed by Grimme was used to involve weak dispersion interactions within the DFT calculations. The reaction energy paths were generated by the minimum energy path calculations using the NEB method.

Analysis of The Main NBR-ISO Standards in The Implementation of An Integrated Management System For Environment, Health, and Occupational Safety

Purpose: This research aims to provide companies with valuable insights into the implementation of an Integrated Management System (IMS), offering a straightforward and practical approach that addresses both environmental and occupational safety aspects. Design/methodology/approach: This study is based on qualitative research aimed at exploring and analyzing Management Systems to gain a deeper understanding of the requirements of the NBR ISO 14001:2015 and NBR ISO 45001:2018 standards. It emphasizes the use of the SWOT analysis (Strengths, Weaknesses, Opportunities, and Threats) to identify areas for organizational improvement, along with the PDCA cycle (Plan - Do - Check - Act) as a strategic tool for system control and continuous improvement. Additionally, the study investigates the key factors that facilitate or hinder the implementation of these standards using the Root Cause Analysis method. Findings: An analysis of the NBR ISO 14001:2015 and NBR ISO 45001:2018 standards in the implementation of an IMS revealed that the SWOT matrix and the PDCA cycle are essential tools for effective planning. The study concludes that successful system implementation requires not only a thorough understanding of the standards' criteria but also a robust organizational culture that supports compliance and continuous improvement. Discussion: Management systems based on the NBR ISO 14001:2015 and NBR ISO 45001:2018 standards have experienced growing market demand. Implementing these systems is crucial for maintaining a company's competitiveness. However, the complexity of their structure and the associated high costs present significant barriers for many organizations, limiting their ability to compete with more established firms.

Optimizing Forward Drop and Reverse Leakage Trade‐Off in AlGaN/GaN Lateral Diode with Schottky‐Metal‐Insulator‐Semiconductor Cascode Anode

Herein, AlGaN/GaN lateral diode with the Schottky‐Metal‐Insulator‐Semiconductor (MIS) cascode anode (CALD) to optimize forward voltage drop (VF) and reverse leakage current (ILEAK) trade‐off is proposed. In the CALD device, a normally‐on Ni/HfO2/AlGaN MIS‐controlled channel as well as a lateral Ni/GaN Schottky contact are cascoded at the anode. The designed normally‐on MIS‐controlled channel has high electron concentration at forward bias and prevents high electric‐field at reverse bias, which ensure both low VF and low ILEAK. Meanwhile, the Ni/GaN Schottky contact with a high Schottky barrier height further suppresses the ILEAK. As a result, the fabricated CALD demonstrates an optimized VF–ILEAK trade‐off relationship, including a low VF of 1.6 V and a low ILEAK of 5.2 × 10−8 A mm−1 (at reverse voltage of 400 V), together with a high breakdown voltage (BV) >700 V. These high performances suggest that the CALD can be a promising candidate for GaN power diode applications requiring a better VF–ILEAK trade‐off.

Small Molecule Activation at the acriPNP Pincer-Supported Nickel Sites.

ConspectusNickel pincer systems have recently attracted much attention for applications in various organometallic reactions and catalysis involving small molecule activation. Their exploration is in part motivated by the presence of nickel in natural systems for efficient catalysis. Among such systems, the nickel-containing metalloenzyme carbon monoxide dehydrogenase (CODH) efficiently and reversibly converts CO2 to CO at its active site. The generated CO moves through a channel from the CODH active site and is transported to a dinuclear nickel site of acetyl-coenzyme A synthase (ACS), which catalyzes organometallic C-S and C-C bond forming reactions. An analogous C-S bond activation process is also mediated by the nickel containing enzyme methyl-coenzyme M reductase (MCR). The nickel centers in these systems feature sulfur- and nitrogen-rich environments, and in the particular case of lactate racemase, an organometallic nickel pincer motif revealing a Ni-C bond is observed. These bioinorganic systems inspired the development of several nickel pincer scaffolds not only to mimic enzyme active sites and their reactivity but also to further extend low-valent organonickel chemistry. In this Account, we detail our continuing efforts in the chemistry of nickel complexes supported by acridane-based PNP pincer ligands focusing on our long-standing interest in biomimetic small molecule activation. We have employed a series of diphosphinoamide pincer ligands to prepare various nickel(II/I/0) complexes and to study the conversion of C1 chemicals such as CO and CO2 to value-added products. In the transformation of C1 chemicals, the key C-O bond cleavage and C-E bond (E = C, N, O, or S, etc.) formation steps typically require overcoming high activation barriers. Interestingly, enzymatic systems overcome such difficulties for C1 conversion and operate efficiently under ambient conditions with the use of nickel organometallic chemistry. Furthermore, we have extended our efforts to the conversion of NOx anions to NO via the sequential deoxygenation by nickel mediated carbonylation, which was applied to catalytic C-N coupling to produce industrially important organonitrogen compound oximes as a strategy for NOx conversion and utilization (NCU). Notably, the rigidified acriPNP pincer backbone that enforces a planar geometry at nickel was found to be an important factor for diversifying organometallic transformations including (a) homolysis of various σ-bonds mediated by T-shaped nickel(I) metalloradical species, (b) C-H bond activation mediated by a nickel(0) dinitrogen species, (c) selective CO2 reactivity of nickel(0)-CO species, (d) C-C bond formation at low-valent nickel(I or 0)-CO sites with iodoalkanes, and (e) catalytic deoxygenation of NOx anions and subsequent C-N coupling of a nickel-NO species with alkyl halides for oxime production. Broadly, our results highlight the importance of molecular design and the rich chemistry of organonickel species for diverse small molecule transformations.

Principles of designing electrocatalysts to boost C–N coupling reactions for urea synthesis

AbstractThe electrocatalytic C–N coupling reaction can achieve green and sustainable urea synthesis as well as CO2 conversion and nitrogen fixation. However, the electrocatalytic C–N coupling reaction still faces challenges such as difficult adsorption and activation of reactive species, a large number of reactive intermediates, high reaction energy barriers, and inert reactive kinetics, resulting in the low urea yielding rate and Faradic efficiency. The development of efficient catalysts is key to improve the urea yielding rate and Faradic efficiency. This review covers the development history and basic principles of electrocatalytic C–N coupling for urea production, analyzes the nanostructure–catalytic activity relationship as well as the electronic structure–catalytic activity relationship, and discusses the main reaction mechanism of electrocatalytic C–N coupling for urea production. Based on these analyses, the concept of designing efficient C–N coupling catalysts is derived. Finally, the research status of electrocatalytic C–N coupling for urea synthesis is summarized, and the prospect for developing efficient electrocatalysts and C–N coupling mechanism are proposed.

Rational Design of Diatomic Active Sites for Elucidating Oxygen Evolution Reaction Performance Trends.

Diatomic catalysts, especially those with heteronuclear active sites, have recently attracted significant attention for their advantages over single-atom catalysts in reactions with relatively high energy barrier, e.g. oxygen evolution reaction. Rational design and synthesis of heteronuclear diatomic catalysts are of immense significance but have so far been plagued by the lack of a definitive correlation between structure and catalytic properties. Here, we report macrocyclic precursor constrained strategy to fabricate series of transition metal (MT, Ni, Co, Fe, Mn, or Cu)-noble (MN, Ir or Ru) centers in carbon material. One notableperformance trend is observed in the order of Cu-MN < Mn-MN < Fe-MN < MN < Co-MN < Ni-MN. However, thepathway has been not altered, still following the traditional adsorption reaction mechanism. The effect of the MT atoms on theperformances could possibly originate from the distinct adsorption/desorption behaviors of key intermediates (i.e. *OH, *O and/or *OOH), strongly implying that ΔG*OOH-ΔG*OH could be used as the performance descriptor. We believe that our work provides useful strategy for synthesis of diatomic active sites with sole coordination configuration and varied composition, and in-depth insight to their catalytic mechanism, which could be used for further optimization of diatomic catalysts towards oxygen electrocatalysis.

Chiral Nanostructured Ag Films for Multicarbon Products from CO2 Electroreduction.

The formation of multicarbon products from CO2 electroreduction is challenging on materials other than Cu-based catalysts. Ag has been known to be a typical metal catalyst, producing CO in CO2 electroreduction. The formation of C2+ products by Ag has never been reported because the carbon-carbon (C-C) coupling is an unfavorable process due to the high reaction barrier energy of *OCCO. Here, we propose that the chirality-induced spin polarization of chiral nanostructured Ag films (CNAFs) can promote the formation of triplet OCCO by regulating its parallel electron spin alignment, and the helical lattice distortion of nanostructures can decrease the reaction energy of *OCCO, which triggers C-C coupling and promotes subsequent *OCCO hydrogenation to facilitate the generation of C2+ products. The CNAFs with helically lattice-distorted nanoflakes were fabricated via electrodeposition using phenylalanine as the symmetry-breaking agent. C2+ products (C2H4, C2H6, C3H8, C2H5OH, and CH3COOH) with a Faradaic efficiency of ∼4.7% and a current density of ∼22 mA/cm2 were generated in KHCO3 electrolytes under 12.5 atm of CO2 (g). Our findings propose that the chiral nanostructured materials can regulate the multifunctionality of catalytic performance in the catalytic reactions with triplet intermediates and products.

Intermolecular Proton Transfer Enabled Reactive CO2 Capture by the Malononitrile Anion.

Task-specific ionic liquids (ILs) employing carbanions represent a new class of ILs for carbon capture. The deprotonated malononitrile carbanion, [CH(CN)2]-, has shown close to equimolar capacity for reactive CO2 capture. Although the formation of the [C(CN)2COOH]- carboxylic acid was found to be the final product, how the hydrogen atom on the [CH(CN)2]- carbanion transfers to the carboxylate group as a proton has not been fully understood. In this work, we employ density functional theory calculations with an implicit solvation model to investigate the proton transfer mechanisms in forming carboxylic acid from the reaction of the [CH(CN)2]- carbanion with CO2. We find that the intramolecular proton-transfer pathway in [CH(CN)2COO]- to form [C(CN)2COOH]- is unlikely due to the high energy barrier of 152 kJ/mol. Instead, the intermolecular proton transfer pathway between two [CH(CN)2COO]- anions is more feasible to form two molecules of [C(CN)2COOH]-, with a significantly lower activation energy of 50 kJ/mol. Moreover, the [C(CN)2COOH]- dimer is further stabilized by the intermolecular hydrogen bonds of the two -COOH groups in the Z-configuration of the π-conjugated planar geometry. This insight of reactive CO2 capture enabled by intermolecular proton transfer will be useful in designing novel carbanions and ILs for carbon capture and conversion.

Preparation and interdiffusion behaviour of a NiCrAlY coating with high entropy ceramic diffusion barrier

In order to solve the problem of elemental interdiffusion between the superalloy and coating, the diffusion barrier of (AlCoCrNiRe) and (AlCoCrNiRe)O between the N5 superalloy and NiCrAlY coating was prepared by magnetron sputtering. Isothermal oxidation behaviour of the NiCrAlY coatings with diffusion barrier was evaluated at 1050 °C. The results show that the application of (AlCoCrNiRe) and (AlCoCrNiRe)O diffusion barriers significantly reduced the precipitation of TCP phase in the substrate. (AlCoCrNiRe)O high entropy ceramic diffusion barrier has a better effect of inhibiting interdiffusion because of its own properties and the oxides formed in situ. Furthermore, the NiCrAlY coating with (AlCoCrNiRe)O high entropy ceramic diffusion barrier provides higher resistance to high-temperature oxidation for the substrate.

Poly (lactic acid)/Poly (butylene adipate-co-terephthalate) Films with Simultaneous High Oxygen Barrier and Fast Degradation Properties

Although poly (lactic acid) (PLA) is a good environmentally-friendly bio-degradable polymer which is used to substitute traditional petrochemical-based polymer packaging films, the barrier properties of PLA films are still insufficient for high-barrier packaging applications. In this study, oxygen scavenger hydroxyl-terminated polybutadiene (HTPB) and cobalt salt catalyst were incorporated into the PLA/poly (butylene adipate-co-terephthalate) (PLA/PBAT), followed by melting extrusion and three-layer co-extrusion blown film process to prepare the composite films. The oxygen permeability coefficient of the composite film combined with 6 wt% oxygen scavenger and 0.4 wt% catalyst was decreased significantly from 377.00 cc∙mil∙m-2∙day-1∙0.1MPa-1 to 0.98 cc∙mil∙m-2∙day-1∙0.1MPa-1, showing a remarkable enhancement of 384.69 times compared with the PLA/PBAT composite film. Meanwhile, the degradation behavior of the composite film was also accelerated, exhibiting a mass loss of nearly 60% of the original mass after seven days of degradation in an alkaline environment, whereas PLA/PBAT composite film only showed a mass loss of 32%. This work has successfully prepared PLA/PBAT composite films with simultaneously improved oxygen barrier property and degradation behavior, which has great potential for high-demanding green chemistry packaging industries, including food, agricultural, and military packaging.

P-tuned FeN2 binuclear sites for boosted CO2 electro-reduction

The recycling of CO2 through electrochemical processes offers a promising solution for alleviating the greenhouse effect; however, the activation of CO2 and desorption of *CO in electrocatalytic CO2 reduction (ECR) frequently encounter high energy barriers and competitive hydrogen evolution reactions (HERs), which are urgent problems that need to be addressed. In this study, a catalyst (P100–Fe–N/C) with homogeneous P–tuned FeN2 binuclear sites (N2PFe-FePN2) was successfully synthesised, demonstrating satisfactory performance in the ECR to CO. P100–Fe–N/C attains a peak FECO of 98.01% and a normalized TOF of 664.7 h-1 at −0.7 VRHE, surpassing the performance of the Fe binuclear catalyst without P and single-atoms catalysts. In the MEA cell, a FECO exceeding 90% can still be achieved. Density functional theory analysis indicates that the asymmetric coordination configuration induced by the incorporation of P facilitates a reduction in the system’s energy. The modulation of P results in the d-band centre of the catalyst being positioned closer to the Fermi level, which facilitates the interaction of the catalyst with CO2, allowing more electrons to be injected into the CO2 molecule at the Fe binuclear sites and inhibiting the HER. The P–tuned FeN2 binuclear sites effectively lower the *CO desorption barrier.

Identifying Highly Active and Selective Cobalt X-Ides for Electrocatalytic Hydrogenation of Quinoline.

Earth-abundant Co X-ides are emerging as promising catalysts for the electrocatalytic hydrogenation of quinoline (ECHQ), yet challenging due to the limited fundamental understanding of ECHQ mechanism on Co X-ides. This work identifies the catalytic performance differences of Co X-ides in ECHQ and provides significant insights into the catalytic mechanism of ECHQ. Among selected Co X-ides, the Co3O4 presents the best ECHQ performance with a high conversion of 98.2% and 100% selectivity at ambient conditions. The Co3O4 sites present a higher proportion of 2-coordinated hydrogen-bonded water at the interface than other Co X-ides at a low negative potential, which enhances the kinetics of subsequent water dissociation to produce H*. An ideal 1,4/2,3-H* addition pathway on Co3O4 surface with a spontaneous desorption of 1,2,3,4-tetrahydroquinoline is demonstrated through operando tracing and theoretical calculations. In comparison, the Co9S8 sites display the lowest ECHQ performance due to the high thermodynamic barrier in the H* formation step, which suppresses subsequent hydrogenation; while the ECHQ on Co(OH)F and CoP sites undergo the 1,2,3,4- and 4,3/1,2-H* addition pathway respectively with the high desorption barriers and thus low conversion of quinoline. Moreover, the Co3O4 presents a wide substrate scope and allows excellent conversion of other quinoline derivatives and N-heterocyclic substrates.