Oxidation Sites Research Articles

Unraveling Sequential Oxidation Kinetics and Determining Roles of Multi-Cobalt Active Sites on Co3O4 Catalyst for Water Oxidation

The multi-redox mechanism involving multi-sites has great implications to dictate the catalytic water oxidation. Understanding the sequential dynamics of multi-steps in oxygen evolution reaction (OER) cycles on working catalysts is a highly important but challenging issue. Here, using quasi-operando transient absorption (TA) spectroscopy and a typical photosensitization strategy, we succeeded in resolving the sequential oxidation kinetics involving multi-active sites for water oxidation in OER catalytic cycle, with Co3O4 nanoparticles as model catalysts. When OER initiates from fast oxidation of surface Co2+ ions, both surface Co2+ and Co3+ ions are active sites of the multi-cobalt centers for water oxidation. In the sequential kinetics (Co2+ → Co3+ → Co4+), the key characteristic is fast oxidation and slow consumption for all the cobalt species. Due to this characteristic, the Co4+ intermediate distribution plays a determining role in OER activity and results in the slow overall OER kinetics. These insights shed light on the kinetic understanding of water oxidation on heterogeneous catalysts with multi-sites.

Clarification of Photoelectrochemical Oxygen Evolution Sites in TiO2 Nanotube Array Electrodes by PbO2 Deposition Method

TiO2 nanotube (TNT) photoanodes exhibit activity and stability for the oxygen evolution reaction (OER) by photoelectrochemical water oxidation. However, the location of the OER site by the photogenerated holes has not been clarified for the TNT photoanodes, unlike well-studied macrocrystalline photocatalysts. In this study, we performed reactions of TNT photoanodes in a 0.1 M Pb(NO3)2 under UV irradiation. The photoelectrochemically deposited PbO2 particles were observed through scanning electron microscopy in the backscattered electron mode. We found that β-PbO2 was deposited on the nanotubes with photocurrent decay and that the reaction site was located on the upper part (∼1 μm) of the TNT array with ∼3 μm length. The photocurrent decay implies the selective deposition of PbO2 on the catalytic site for water oxidation. The PbO2 nanoparticles were deposited on the inner and outer surfaces of the tube walls. This result is consistent with the mechanism of charge separation at the space charge layers formed on both surfaces of the walls. We also confirmed that the OER site changes depending on the wavelength of the incident light due to the change in the light penetration depth.

Selective sensing performance of UV-activated ZnO nanowires decorated with Ir and Rh nanoparticles

Single-crystal zinc oxide (ZnO) nanowires (NWs) were synthesized through self-assembly hydrothermal reaction and decorated with oxidative and reductive catalytic active sites to tailor their gas sensing selectivity. The sensing performances of the developed materials were investigated under ultraviolet-light emitting diode (UV-LED) irradiation against low concentrations of nitrogen dioxide (NO2) and ammonia (NH3) gases, as oxidizing and reducing gas representatives, respectively. The growth of NWs towards the hexagonal c-axis was demonstrated, where presence of Rh3d and Ir4f active sites on the surface of ZnO NWs was observed. The sensing performance of the surface modified ZnO NWs was enhanced significantly, compared with that of the pristine ZnO NWs. The Rh-decorated ZnO NWs sensor exhibited superior performance in the detection of NO2, while the Ir sites promoted the oxidative reaction in the presence of NH3, attributed to the Fermi level of the metal-decorated films under UV irradiation.

Protection mechanism of N,N-dimethylformamide on stability of few-layer black phosphorus

Few-layer black phosphorus (LBP) has been widely investigated for its unique optical and electronic properties. As degradation of LBP in ambient conditions largely limited its practical applications, numerous stabilization methods were developed. Understanding stabilization mechanism is essential to development of new protection technologies for LBP. Herein, protection mechanism of the most wildly used exfoliation solvent N,N-dimethylformamide (DMF) on LBP was investigated. DMF was found to accelerate color fading of LBP in aerobic water solution. Nevertheless, dissolvable phosphorus generated from degradation of LBP in the presence of DMF accounted for only 52%–57% of that generated in the absence of DMF. By measuring kinetics constants and activation energies of the degradation reactions, the protection mechanism of DMF was attributed to impede hydrolysis of phosphorus oxides. This was caused by occupation of oxidation sites on LBP by DMF through electrostatic interaction. Insoluble phosphorus oxides in addition to dissolvable phosphorus were observed in DMF exfoliated LBP aqueous solution, providing further evidence for hydrolysis impeding mechanism. This finding threw mechanism light on protection effects of DMF on LBP, providing new knowledge for development of effective stabilization technologies of LBP.

Rapid synthesis of MgCo2O4: Morphology control, defect modulation, activity enhancement and applications

Organic fuels are the main factors affecting the morphology, pore structure and catalytic active sites of metal oxides in solution combustion synthesis (SCS). However, due to the diversity of organic fuel structures, the specific role of organic fuel types on SCS is questionable. In this work, we compared the effects of five organic fuels on the thermocatalytic active sites of graded porous MgCo2O4 nanomaterials. MgCo2O4 (CA-MCO) prepared with citric acid as fuel has the largest specific surface area and the richest pore structure with the largest number of active sites. And the porous CA-MCO exhibited the best catalytic properties that the THTD of AP decreased by 206.06 °C, the activation energy (Ea) decreased by 104.58 kJ·mol−1, and the reaction rate (k) increased by 2.49 s−1. A possible catalytic mechanism for the thermal decomposition of AP was also proposed based on TG-MS and Hall effect tests. Finally, CA-MCO was applied to AP/HTPB-based composite solid propellants (CSPs), and the results showed that the introduction of CA-MCO significantly shortened the ignition delay time of the CSPs (From 29 ms to 8 ms), indicating its potential application in the CSPs.

CaMKII-Dependent Contractile Dysfunction and Pro-Arrhythmic Activity in a Mouse Model of Obstructive Sleep Apnea.

Left ventricular contractile dysfunction and arrhythmias frequently occur in patients with sleep-disordered breathing (SDB). The CaMKII-dependent dysregulation of cellular Ca homeostasis has recently been described in SDB patients, but these studies only partly explain the mechanism and are limited by the patients' heterogeneity. Here, we analyzed contractile function and Ca homeostasis in a mouse model of obstructive sleep apnea (OSA) that is not limited by confounding comorbidities. OSA was induced by artificial tongue enlargement with polytetrafluorethylene (PTFE) injection into the tongue of wildtype mice and mice with a genetic ablation of the oxidative activation sites of CaMKII (MMVV knock-in). After eight weeks, cardiac function was assessed with echocardiography. Reactive oxygen species (ROS) and Ca transients were measured using confocal and epifluorescence microscopy, respectively. Wildtype PTFE mice exhibited an impaired ejection fraction, while MMVV PTFE mice were fully protected. As expected, isolated cardiomyocytes from PTFE mice showed increased ROS production. We further observed decreased levels of steady-state Ca transients, decreased levels of caffeine-induced Ca transients, and increased pro-arrhythmic activity (defined as deviations from the diastolic Ca baseline) only in wildtype but not in MMVV PTFE mice. In summary, in the absence of any comorbidities, OSA was associated with contractile dysfunction and pro-arrhythmic activity and the inhibition of the oxidative activation of CaMKII conveyed cardioprotection, which may have therapeutic implications.

Cobalt oxide functionalized ceramic membrane for 4-hydroxybenzoic acid degradation via peroxymonosulfate activation

Membrane separation and sulfate radicals-based advanced oxidation processes (SR-AOPs) can be combined as an efficient technique for the elimination of organic pollutants. The immobilization of metal oxide catalysts on ceramic membranes can enrich the membrane separation technology with catalytic oxidation avoiding recovering suspended catalysts. Herein, nanostructured Co3O4 ceramic catalytic membranes with different Co loadings were fabricated via a simple ball-milling and calcination process. Uniform distribution of Co3O4 nanoparticles in the membrane provided sufficient active sites for catalytic oxidation of 4-hydroxybenzoic acid (HBA). Mechanistic studies were conducted to determine the reactive radicals and showed that both SO4•− and •OH were present in the catalytic process while SO4•− plays the dominant role. The anti-fouling performance of the composite Co@Al2O3 membranes was also evaluated, showing that a great flux recovery was achieved with the addition of PMS for the fouling caused by humic acid (HA).

Nanoscale chemical and structural investigation of solid solution polyelemental transition metal oxide nanoparticles

Although it has been shown that configurational entropy can improve the structural stability in transition metal oxides (TMOs), little is known about the oxidation state of transition metals under random mixing of alloys. Such information is essential in understanding the chemical reactivity and properties of TMOs stabilized by configurational entropy. Herein, utilizing electron energy loss spectroscopy (EELS) technique in an aberration-corrected scanning transmission electron microscope (STEM), we systematically studied the oxidation state of binary (Mn,Fe)3O4, ternary (Mn, Fe, Ni)3O4, and quinary (Mn, Fe, Ni, Cu, Zn)3O4 solid solution polyelemental transition metal oxides (SSP-TMOs) nanoparticles. Our findings show that the random mixing of multiple elements in the form of solid solution phase not only promotes the entropy stabilization but also results in stable oxidation state in transition metals spanning from binary to quinary transition metal oxide nanoparticles.

Construction of graphdiyne (CnH2n-2) based Co-S-P/CuI double S-scheme heterojunctions proved with in situ XPS characterization for efficient photocatalytic hydrogen production

Graphdiyne (GDY) is a novel two-dimensional carbon isomeric material with a high π⁃conjugation and good electrical conductivity, a tunable natural band gap. Here, the promotion of GDY on the photocatalytic system is investigated by preparing Co-S-P/CuI double S-scheme heterojunctions based on graphdiyne (CnH2n-2). The Co-S-P rough nanosheet structure provides a large number of aiming points for CuI nanoblocks, which effectively prevents the aggregation of CuI nanoblocks. It not only provides a large number of active sites for the reaction, but also facilitates the visible light injection. When GDY is introduced, the three-dimensional structure of GDY/CuI is tightly attached to the Co-S-P surface. On the one hand, the unique two-dimensional/three-dimensional structure is beneficial to promote the mass transfer properties between Co-S-P, GDY and CuI and improve the absorption of visible light. On the other hand, the unique lamellar structure of GDY is like a “tape” connecting Co-S-P and CuI, which not only makes the bond between Co-S-P and CuI tighter, but also serves as a “fabric” to isolate the oxidation sites on the surface of Co-S-P. As a result, the ternary catalyst exhibits excellent hydrogen precipitation stability and photocorrosion resistance. Under 5 W (λ > 420 nm) LED light, CSPGC-20 (135.49 μmol) exhibited the best hydrogen precipitation activity, which is 26.22, 9.2 and 1.6 times higher than that of GDY/CuI (5.32 μmol), Co-S-P (14.72 μmol) and CSPC-20 (85.08 μmol), respectively. This experiment demonstrates the promising potential of Graphdiyne (GDY) for photocatalytic water splitting.

Insights into peptide profiling of sturgeon myofibrillar proteins with low temperature vacuum heating.

Protein oxidation during food processing causes changes in the balance of protein-molecular interactions and protein-water interactions, ultimately leading to protein denaturation, which results in the loss of a range of functional properties. Therefore, how to control the oxidative modification of proteins during processing has been the focus of research. In the present study, the intrinsic fluorescence value of the myofibrillar proteins (MP) decreased and the surface hydrophobicity value increased, indicating that the heat treatment caused a significant change in the conformation of the MP. With an increase in heating temperature, protein carbonyl content increased, total sulfhydryl content decreased, and protein secondary structure changed from α-helix to β-sheet, indicating that protein oxidation and aggregation occurred. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis revealed that heat treatment can lead to the degradation of proteins, especially myosin heavy chain, although actin had a certain thermal stability. In total, 733 proteins were identified by proteomics, and the protein oxidation caused by low temperature vacuum heating (LTVH) was determined to be mild oxidation dominated by malondialdehyde and 4-hydroxynonenal by oxidation site division. The present study has revealed the effect of LTVH treatment on the protein oxidation modification behavior of sturgeon meat, and explored the effect mechanism of LTVH treatment on the processing quality of sturgeon meat from the perspective of protein oxidation. The results may provide a theoretical basis for the precise processing of aquatic products. © 2023 Society of Chemical Industry.

Elucidating the crystal-facet dependent catalytic performance of coupled flake-CuO/Cu-zeolite hybrid catalysts for coal-gas-SCR

Multi-active sites were usually molded to achieve better catalytic performance for those reactions involving multiple reactants. In this work, CuO/Cu-ZSM-5 (CuO/Cu-Z5) hybrid catalysts with structurally well-defined CuO nanoparticles and site-isolated Cu ions were synthesized and applied for selective catalytic reduction by coal-gas (coal-gas-SCR). The activity evaluation reveals that participation of CuO could significantly improve NOx conversion of Cu-Z5, and Flake-CuO nanoparticle exhibits the best catalytic performance. Several comprehensive characterizations manifest that Flake-CuO/Cu-Z5 contains the highest density of oxygen vacancies, on which the richly exposed CuO (200) facet shows high oxygen mobility and low oxygen vacancy formation energy that verified by DFT calculation. Additionally, Flake-CuO provides superior redox ability and highly active sites for NO adsorption and oxidation to NO2, which can remarkably accelerate subsequent SCR rates. In situ DRIFTS demonstrates that more adsorbed NO2 and bidentate nitrate species generated on Flake-CuO/Cu-Z5, and the amount of other vital intermediate species (such as NHx and CH3NO) were also largely formed over the sample. Interestingly, after injecting reductants, the bidentate nitrate on Rod-CuO/Cu-Z5, Sheet-CuO/Cu-Z5, and Cu-Z5 is partially transformed to monodentate nitrate, whereas Flake-CuO/Cu-Z5 could prohibit this process due to those substantial chemisorbed oxygen and appropriate adsorption ability of intermediates species over CuO (200) facet. The mass migration between CuO and Cu2+ ions revealed that CuO (200) facet not only catalyzes the SCR reaction but also could transfer those formed nitrates and activated reactants to Cu2+ ions in zeolite framework nearby to accomplish the following reaction, fulfilling the acceleration of SCR process.

Tailored Synthesis of Catalytically Active Cerium Oxide for N, N-Dimethylformamide Oxidation.

Cerium oxide nanopowder (CeOx) was prepared using the sol-gel method for the catalytic oxidation of N, N-dimethylformamide (DMF). The phase, specific surface area, morphology, ionic states, and redox properties of the obtained nanocatalyst were systematically characterized using XRD, BET, TEM, EDS, XPS, H2-TPR, and O2-TPO techniques. The results showed that the catalyst had a good crystal structure and spherelike morphology with the aggregation of uniform small grain size. The catalyst showed the presence of more adsorbed oxygen on the catalyst surface. XPS and H2-TPR have confirmed the reduction of Ce4+ species to Ce3+ species. O2-TPR proved the reoxidability of CeOx, playing a key role during DMF oxidation. The catalyst had a reaction rate of 1.44 mol g-1cat s-1 and apparent activation energy of 33.30 ± 3 kJ mol-1. The catalytic performance showed ~82 ± 2% DMF oxidation at 400 °C. This work's overall results demonstrated that reducing Ce4+ to Ce3+ and increasing the amount of adsorbed oxygen provided more suitable active sites for DMF oxidation. Additionally, the catalyst was thermally stable (~86%) after 100 h time-on-stream DMF conversion, which could be a potential catalyst for industrial applications.

Revealing the Selective Bifunctional Electrocatalytic Sites via In Situ Irradiated X-Ray Photoelectron Spectroscopy for Lithium-Sulfur Battery.

The electrocatalysts are widely applied in lithium-sulfur (Li-S) batteries to selectively accelerate the redox kinetics behavior of Li2 S, in which bifunctional active sites are established, thereby improving the electrochemical performance of the battery. Considering that the Li-S battery is a complex closed "black box" system, the internal redox reaction routes and active sites cannot be directly observed and monitored especially due to the distribution of potential active-site structures and their dynamic reconstruction. Empirical evidence demonstrates that traditional electrochemical test methods and theoretical calculations only probe the net result of multi-factors on an average and whole scale. Herein, based on the amorphous TiO2- x @Ni selective bifunctional model catalyst, these limitations are overcome by developing a system that couples the light field and in situ irradiated X-ray photoelectron spectroscopy to synergistically convert the "black box" battery into a "see-through" battery for direct observation of the charge transportation, thus revealing that amorphous TiO2- x and Ni nanoparticle as the oxidation and reduction sites selectively promote the decomposition and nucleation of Li2 S, respectively. This work provides a universal method to achieve a deeper mechanistic understanding of bidirectional sulfur electrochemistry.

Ablation of CaMKIIδ oxidation by CRISPR-Cas9 base editing as a therapy for cardiac disease.

CRISPR-Cas9 gene editing is emerging as a prospective therapy for genomic mutations. However, current editing approaches are directed primarily toward relatively small cohorts of patients with specific mutations. Here, we describe a cardioprotective strategy potentially applicable to a broad range of patients with heart disease. We used base editing to ablate the oxidative activation sites of CaMKIIδ, a primary driver of cardiac disease. We show in cardiomyocytes derived from human induced pluripotent stem cells that editing the CaMKIIδ gene to eliminate oxidation-sensitive methionine residues confers protection from ischemia/reperfusion (IR) injury. Moreover, CaMKIIδ editing in mice at the time of IR enables the heart to recover function from otherwise severe damage. CaMKIIδ gene editing may thus represent a permanent and advanced strategy for heart disease therapy.

High-resolution cryo-EM structures of plant cytochrome b6f at work.

Plants use solar energy to power cellular metabolism. The oxidation of plastoquinol and reduction of plastocyanin by cytochrome b6f (Cyt b6f) is known as one of the key steps of photosynthesis, but the catalytic mechanism in the plastoquinone oxidation site (Qp) remains elusive. Here, we describe two high-resolution cryo-EM structures of the spinach Cyt b6f homodimer with endogenous plastoquinones and in complex with plastocyanin. Three plastoquinones are visible and line up one after another head to tail near Qp in both monomers, indicating the existence of a channel in each monomer. Therefore, quinones appear to flow through Cyt b6f in one direction, transiently exposing the redox-active ring of quinone during catalysis. Our work proposes an unprecedented one-way traffic model that explains efficient quinol oxidation during photosynthesis and respiration.

Elimination of NH3 by Interfacial Charge Transfer over the Ag/CeSnOx Tandem Catalyst

Selective catalytic oxidation of NH3 is the most promising method for removing low-concentration NH3. However, achieving high activity and N2 selectivity remains a great challenge. A Ag/CeSnOx tandem catalyst with dual active centers was designed and synthesized, which couples the NH3 over-oxidation on the noble metal active sites with NOx reduction on the support. The tandem catalyst exhibited excellent NH3 selective catalytic oxidation (NH3–SCO) performance at 200–400 °C. Based on various characterization techniques and DFT calculations, it was identified that the silver species on the Ag/CeSnOx catalysts existed as AgO nanoparticles (AgO NPs), and the electrons on the support were more easily transferred to AgO NPs, which promoted the oxidation activity of AgO and the reduction performance of the CeSnOx support. The coupling between the AgO NPs and CeSnOx helped balance the NH3 oxidation rate and the NOx reduction rate. In addition, the uniform adsorption of gaseous NH3 on the oxidation and reduction sites was also demonstrated by theoretical calculations, which is a prerequisite for tandem catalysis. By in situ DRIFTS, we revealed that the NH3–SCO reaction over Ag/CeSnOx catalysts mainly follows the internal selective catalytic reduction mechanism. It was characterized by excessive oxidation of NH3 to NOx on AgO NPs. At a temperature lower than 200 °C, NOx was reduced to N2 by the adsorbed NH3 on the AgO. When the temperature was higher than 200 °C, NOx was reduced to N2 by NH3 or NH4+ adsorbed on the CeSnOx support. Therefore, the charge transfer at the Ag/CeSnOx catalyst interface and the coordination of atomic scale catalytic sites have realized the conversion of NH3 to N2 through NOx in a tandem catalytic mode.

Atomic symmetry alteration in carbon nitride to modulate charge distribution for efficient photocatalysis

The periodical distribution of N and C atoms in the carbon nitride skeleton results in intrinsically insufficient light absorption and serious carrier recombination. Herein, an efficient two-step cystine-mediated strategy was developed to alter the structure symmetry of C3N4 via the introduction of alkyl groups and nitrogen vacancies. The experimental analysis and theoretical calculation confirm that the formation of alkyl groups and nitrogen vacancies can modulate band structure and activate n-π* electron transition. Especially, the charge density in CN-25CYS is redistributed with spatial separation of oxidation and reduction sites, suppressing photogenerated charge recombination effectively. Therefore, the distorted carbon nitride (CN-25CYS) exhibits 9.6-times and 15.6-times higher photoreaction rates in hydrogen production and RhB degradation than the pristine one (CN-0CYS), respectively.

The cryoEM structure of cytochrome bd from C. glutamicum provides novel insights into structural properties of actinobacterial terminal oxidases.

Cytochromes bd are essential for microaerobic respiration of many prokaryotes including a number of human pathogens. These enzymes catalyze the reduction of molecular oxygen to water using quinols as electron donors. Their importance for prokaryotic survival and the absence of eukaryotic homologs make these enzyme ideal targets for antimicrobial drugs. Here, we determined the cryoEM structure of the menaquinol-oxidizing cytochrome bd-type oxygen reductase of the facultative anaerobic Actinobacterium Corynebacterium glutamicum at a resolution of 2.7Å. The obtained structure adopts the signature pseudosymmetrical heterodimeric architecture of canonical cytochrome bd oxidases formed by the core subunits CydA and CydB. No accessory subunits were identified for this cytochrome bd homolog. The two b-type hemes and the oxygen binding heme d are organized in a triangular geometry with a protein environment around these redox cofactors similar to that of the closely related cytochrome bd from M. tuberculosis. We identified oxygen and a proton conducting channels emerging from the membrane space and the cytoplasm, respectively. Compared to the prototypical enzyme homolog from the E. coli, the most apparent difference is found in the location and size of the proton channel entry site. In canonical cytochrome bd oxidases quinol oxidation occurs at the highly flexible periplasmic Q-loop located in the loop region between TMHs six and seven. An alternative quinol-binding site near heme b 595 was previously identified for cytochrome bd from M. tuberculosis. We discuss the relevance of the two quinol oxidation sites in actinobacterial bd-type oxidases and highlight important differences that may explain functional and electrochemical differences between C. glutamicum and M. tuberculosis. This study expands our current understanding of the structural diversity of actinobacterial and proteobacterial cytochrome bd oxygen reductases and provides deeper insights into the unique structural and functional properties of various cytochrome bd variants from different phylae.

All-Solid-State C3N4/NixP/Red Phosphorus Z-Scheme Heterostructure for Wide-Spectrum Photocatalytic Pure Water Splitting

Z-scheme photocatalysts encouraged by natural photosynthesis have received increasing attention for pure water splitting. However, there have been only a few instances of effective Z-scheme nanosystems utilizing nonmetal photocatalysts for both water reduction and oxidation. In this study, we used carbon nitride (CN), metallic NixP, and crystalline red phosphorus (RP) to build a solid-state Z-scheme photocatalytic system, which worked as reduction sites, an electron mediator, and oxidation sites, respectively. The light absorption capability up to ∼600 nm enabled the photocatalyst to realize water splitting under broad-spectrum illumination. Detailed analysis suggested that the photocatalytic hydrogen production rate was apparently enhanced on account of effective spatial separation of light-induced charges owing to the intimate contact between the NixP mediator and photocatalyst components as well as the suitable energy band alignment. Meanwhile, hydrogen peroxide instead of oxygen was generated from water oxidation, which can solve the separation and safety issues of the synchronized production of hydrogen and oxygen and thus facilitated the feasible application of photocatalytic hydrogen production.

Polyoxovanadate-based metal–organic frameworks consisted of open vanadium sites for selective catalytic oxidation of sulfides

Polyoxovanadate-based metal–organic frameworks consisted of open vanadium sites for selective catalytic oxidation of sulfides