Oxidation Sites Research Articles

Challenging design of highly active Pt/CeO2–TiO2/ZSM-5 catalysts for VOCs low-temperature removal

Four Pt/CeO2–TiO2/ZSM-5 catalysts with different Pt species dispersion states and acidic properties were designed, and key factors affecting the oxidation activity of various VOCs (benzene, DCE, ethyl acetate and acetonitrile as typical organic compounds of aromatic hydrocarbon and halogen/oxygen/nitrogen-containing VOCs, respectively) were identified in the present work. The strength of the acid and oxidation sites on the surface of catalysts and their synergistic interaction play a crucial role. Highly dispersed Pt species and its strong redox ability promote low-temperature oxidation of benzene. A synergistic interaction between the acid and oxidation sites is required to achieve high DCE oxidation activity. An abundance of surface acid sites (particularly strong acid sites) favors the adsorption and dechlorination to form vinyl chloride of DCE, and the strong redox ability of oxidation sites would accelerate the deep oxidation of intermediates (such as vinyl chloride and acetic acid, etc.). For ethyl acetate or acetonitrile oxidation, the strong acidic property of the catalyst plays a prior role for their catalytic oxidation, which facilitates the low-temperature hydrolysis of ethyl acetate or acetonitrile. This work provides a significant thought to design and synthesize high activity catalysts for low-temperature oxidation of various VOCs pollutants.

Exploring Oxygen Vacancy Effect in 1D Structural SnIP for CO2 Electro-Reduction to Formate.

1D nanostructures exhibit a large surface area and a short network distance, facilitating electron and ion transport. In this study, a 1D van der Waals material, tin iodide phosphide (SnIP), is synthesized and used as an electrocatalyst for the conversion of CO2 to formate. The electrochemical treatment of SnIP reconstructs it into a web-like structure, dissolves the I and P components, and increases the number of oxygen vacancies. The resulting oxygen vacancies promote the activity of the CO2 reduction reaction (CO2RR), increasing the local pH of the electrode surface and maintaining the oxidative metal site of the catalyst despite the electrochemically reducing environment. This strategy, which stabilizes the oxidation state of the catalyst, also helps to improve the durability of CO2RR. In practice, 1D structured SnIP catalyst exhibits outstanding performance with >92% formate faradaic efficiency (FEformate) at 300mAcm-2, a maximum partial current density for formate of 343mAcm-2, and excellent long-term stability (>100h at 100mAcm-2 with >86% FEformate). This study introduced a method to easily generate oxygen vacancies on the catalyst surface by utilizing 1D materials and a strategy to improve the durability of CO2RR by stabilizing the oxidation state of the catalyst.

Direct Production of Sustainable Aviation Fuel by Deoxygenation and Isomerization of Triglycerides Over Bifunctional Ir-ReOx/SAPO-11 Catalyst.

Catalytic thermochemical conversion offers a sustainable method to upgrade oil-based feedstocks into highly valuable biofuel, aligning with the modern biorefinery concept. Herein, a series of IrRe/SAPO-11 catalysts with different Ir to Re molar ratios compared to reference Ir/SAPO-11 and Re/SAPO-11 catalysts was prepared using a wetness impregnation method. These catalysts were used for the direct production of sustainable aviation fuels (SAFs) via efficient hydrodeoxygenation and hydroisomerization of triglycerides. The catalyst screening confirmed that the optimum IrRe/SAPO-11 catalyst, with an equivalent Ir to Re molar ratio, exhibited the highest hydrodeoxygenation activity under milder operation conditions than the conditions used in previous studies. Increasing the reaction temperature up to 330 °C enhanced the formation of iso-alkanes in the liquid product, achieving a freezing point of -31.4 °C without additional cold flow improvers. Furthermore, a long-term stability experiment demonstrated that the developed Ir-Re system exhibited exceptional performance over 150 h. This excellent catalytic activity and stability of the bifunctional IrRe/SAPO-11 catalyst was owing to its suitable interface between metallic and oxide sites, mixed mesoporous structures, reduced catalyst size, and increased Lewis acid ratio, as confirmed by our comprehensive characterizations.

Single step grown porous polycrystalline nickel microstructures with ultra-thin defect rich surface oxide for alkaline water oxidation

Investigation on the intrinsic catalytic activity of structurally diverse polycrystalline nickel microstructures such as porous nickel sheets (PNS), porous folded/curled nickel structures (PFNS) and porous nickel balls (PNB) revealed the surface bounded electrocatalytic activities within an alkaline reaction environment for water oxidation. Nickel microstructures were grown via template/surfactant-free, single step solution combustion technique in air atmosphere. The distinct morphologies (porous nickel sheets, porous folded/curled nickel structures and porous nickel balls) were achieved through changing the quantity of HNO3 in the reaction mixture. The physicochemical characterisations were done with XRD, FESEM, EDS and XPS. Microscopic studies revealed the growth of nickel grains with numerous macro pores forming microstructures in distinct morphologies. The O ls spectra of XPS studies revealed the presence of O−/O2− sites and Ni 2p spectra were distinguished between the formation of Ni0/Ni2+/Ni3+ states, implied the existence of surface oxide with plenty of defects. The synergistic effect results from the formation of microscopic porous architectures with defect rich surface oxide on the electrochemical behaviour and OER activity of PNS, PFNS and PNB were discussed with electrochemical techniques such as CV, LSV, EIS and CP. The OER kinetics in terms of relatively low value of overpotential at 10 mA cm−2 and Tafel slope along with high specific activity of PNS/GCE with respect to PFNS/GCE and PNB/GCE were attributed to the combined effect of increase in electrochemical surface area, high roughness factor and fast charge transfer kinetics. The better electrochemical performance and OER activities of porous nickel sheets in comparison with folded/curled nickel structures and nickel balls is contributed to the unique 2D porous architecture with plenty of oxygen vacancies. This structure not only expose more surface for the formation of passive oxide layer in an alkaline reaction environment but also exhibit facile charge transport properties, causes the generation of numerous surface-active sites for electrocatalytic water oxidation. The outcome of our work gives new insights on the surface electrochemistry of polycrystalline nickel, enables micro-structuring as a prospective strategy towards the optimization of electrocatalysts as anode material for alkaline water oxidation.

Exploiting Mixed Valence Charge Transfer for Electrochromic and Electrofluorochromic Use.

An asymmetric mixed valence fluorophore with two different electron rich termini was investigated as a dual-role active material for electrochromism and electrofluorochromism. The fluorescence quantum yield (Φfl) and emission wavelength of the fluorophore were dependent on solvent polarity. The quantum yield of the material in an electrolyte gel, on a glass substrate and in a device was 40 %, 20 % and 13 % respectively. The fluorophore further underwent two near-simultaneous electrochemical oxidations. The first oxidation resulted in a 1000 nm red shift in the absorption to broadly absorb in the NIR, corresponding to the intervalence charge transfer (IVCT). Whereas the second oxidation led to a perceived green color at 715 nm with the extinction of the NIR absorbing IVCT. Owing to the dissymmetry of the fluorophore along with its two unique oxidation sites, the IVCT gives rise to a mixed valence transfer charge (MVCT). The coloration efficiency of the fluorophore in both solution and a device was 1433 and 200 cm2 C-1, respectively. The fluorescence intensity could be reversibly modulated electrochemically. The photoemission intensity of the fluorophore was modulated with applied potential in an operating electrochromic/electrofluorochromic device. Both the dual electrochromic and the electrofluorochromic behavior of the fluorophore were demonstrated.

Electrochemically activated metal oxide sites at Rh–Ni2P electrocatalyst for efficient alkaline hydrogen evolution reaction

Electrochemically activated metal oxide sites at Rh–Ni2P electrocatalyst for efficient alkaline hydrogen evolution reaction

Construction of sulfur modified oxygen-deficient NiO/Ni nanoflakes as an effective electrode material for energy storage application

The inferior electronic conductivity and deficient number of electrochemical active sites of the transition metal oxides severely restrict electrode kinetics and the utilization of redox actives sites on the electrode surface, thus leading to ineffective electrochemical performance. Herein, we exhibit an effective strategy to obtain NiO/Ni nanoflakes with oxygen vacancies and sulfur dopants (S-NiO1-x/Ni) for serving as supercapacitor electrode. The incorporation of O vacancies and S dopants into NiO/Ni in concert to modulate the electronic structure and generates more accessible active sites, which improve the electrochemical conductivity and facilitates surface redox processes. Experimental and theoretical studies provide insight into the location of the introduction of O vacancy and S atom and their effects on the electrical properties of S-NiO1-x/Ni. Meanwhile, S atoms incorporation into S-NiO1-x/Ni not only involve in the redox reactions but also act as active sites. The as-obtained S-NiO1-x/Ni delivers a remarkable electrochemical behavior with a high specific capacitance of 648.4F g−1 at the current density of 1 A/g. Additionally, an asymmetric supercapacitor outfitted with the as-prepared S-NiO1-x/Ni as positive electrode and active carbon as negative electrode gives rise to an excellent energy density of 28.8 Wh kg−1 at the power density of 800 W kg−1, together with a long-term stability.

Low-coordinated Mn–N2 sites in graphene oxide induce peroxydisulfate activation for tetracycline degradation: Process optimization and theoretical calculation

Atom-dispersed low-coordinated transition metal-Nx catalysts exhibit excellent efficiency in activating peroxydisulfate (PDS) for environmental remediation. However, their catalytic performance is limited due to metal-N coordination number and single-atom loading amount. In this study, low-coordinated nitrogen-doped graphene oxide (GO) confined single-atom Mn catalyst (Mn-SA/NGO) was synthesized by molten salt-assisted pyrolysis and coupled to PDS for degradation of tetracycline (TC) in water. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) analysis showed the successful doping of single-atom Mn (weight percentage 1.6%) onto GO and the formation of low-coordinated Mn–N2 sites. The optimized parameters obtained by Box-Behnken Design achieved 100% TC removal in both prediction and experimental results. The Mn-SA/NGO + PDS system had strong anti-interference ability for TC removal in the presence of anions. Besides, Mn-SA/NGO possessed good reusability and stability. O2•−, •OH, and 1O2 were the main active species for TC degradation, and the TC mineralization reached 85.1%. Density functional theory (DFT) calculations confirmed that the introduction of single atoms Mn could effectively enhance adsorption and activation of PDS. The findings provide a reference for the synthesis of high-performance single-atom catalysts for effective removal of antibiotics.

A Solid‐Solution with Asymmetric Ni‐O‐Cr Sites for Boosting Protonation toward Anodic Oxidation

AbstractReplacing the slow protonation process of oxygen evolution reaction (OER) with the fast protonation of alcohol electro‐oxidation can decrease the driving potentials, thus improving overall efficiency of electrochemical devices. However, the formation of effective catalytic sites for alcohol oxidation remains challenging in accelerating protonation to inhibit metal leaching and improve catalyst stability. Herein, asymmetric Ni‐O‐Cr sites are constructed by alloying Cr into the NiO matrix to optimize coordination environments, showing significantly enhanced stability during alcohol electro‐oxidation. The asymmetric Ni‐O‐Cr can maintain constant valence states of Cr and Ni during alcohol oxidation, efficiently suppressing metal dissolution even at high oxidation potentials. In situ electrochemical characterizations combined with theoretical calculations indicate that asymmetric Ni‐O‐Cr can improve adsorption and activation of OH* and alcohol molecules compared to pure NiO, thus increasing anodic kinetics. The theoretical results also indicate that the smaller gap of Ni 3d‐O 2p in asymmetric Ni‐O‐Cr strengthens charge transfer, leading to fast protonation of catalytic sites with enhanced stability. This work gives insights into boosting anodic protonation using asymmetric sites‐enriched solid‐solution electrocatalysts.

Molecular-atomic scale insights into polymer-asphalt interactions induced by the oxidation of reactive oxygen species via computational simulation and multifield microscopy characterization

The objective of this study is to investigate the intermolecular interactions between polymers and asphalt components due to the oxidation of reactive oxygen species (ROS). Quantum chemistry (QC) and molecular dynamics (MD) were employed to simulate the molecular properties and intermolecular interactions between SBS and asphalt components during ROS aging. Multifield optical microscopy was utilized to analyze the microstructural characteristics and validate intermolecular interactions of SBS and asphalt components during ROS aging. The results show that asphaltenes have the most uneven electrostatic potential (ESP) distribution, followed by resins and aromatics, while saturates exhibit the most uniform ESP distribution. ROS aging leads to a more uneven ESP distribution and a higher polarity for HiMA molecules, especially for asphaltenes and resins with increased formation of polar functional groups. SBS and saturates exhibit small energy gaps and electronic softness, indicating good resistance to ROS oxidation, whereas asphaltenes and resins are prone to free radical oxidation reactions with ROS. The potential ROS oxidation site of asphaltenes and resins are mainly distributed in benzene ring regions and heteroatoms, while that of SBS are primarily located at the polybutadiene chains. The interactions between SBS and asphalt components are primarily driven by van der Waals forces. However, the hydrogen bonding appears after ROS aging, enhancing the intermolecular interactions. The interaction energies of SBS-asphaltenes and SBS-resins are significantly enhanced, and the intermolecular distances are shortened as ROS aging progresses. Multifield microscopy observation reveals that the development of bee structures in polymer regions is significantly faster than that in asphalt regions, indicating a significantly enhanced adsorption of asphaltenes by polymers after ROS aging. This is attributed to the uneven charge distribution, increased polarity, and enhanced reactivity of asphaltenes and SBS due to ROS aging. This study contributes to a molecular-atomic-level understanding of the intermolecular interactions between polymers and asphalt components during ROS aging.

A switch and a failsafe: KatG’s mechanism for preservation of catalase activity using a conformationally dynamic Arg and an active-site Trp

Many novel structural features impart a robust catalase activity to KatG that is absent from all other members of its superfamily. The conformationally dynamic “Arg switch” and oxidizable “proximal Trp” have both figured prominently in investigations of KatG structure and mechanism, but the full scope of their contributions to catalysis remains unclear. The switch (R418) appears to regulate active-site intramolecular electron transfer. The proximal Trp (W321) is a conspicuous site of radical formation, but W321•+ does not appear to participate directly in the KatG catalase cycle. To explore the extent to which these residues may cooperate in KatG’s catalase activity, we generated R418N and W321F/R418N KatG and compared their catalytic and spectroscopic properties to wt KatG. R418N KatG showed pH-independent susceptibility to H2O2-based inactivation, whereas wt KatG only showed this response under conditions where the Arg switch would be oriented away from the active site (i.e., low pH). Peroxidatic electron donors (PxEDs) prevented inactivation of wt and R418N KatG regardless of pH; however, protection of R418N KatG activity by this mechanism produced at least ten-fold greater extents of PxED oxidation. Elimination of the proximal Trp in addition to the Arg switch (i.e., W321F/R418N KatG) resulted in a near complete inability to sustain H2O2 degradation. Remarkably, W321F KatG showed resistance to H2O2-dependent inactivation indistinguishable from wt at pH 7 (i.e., when the Arg switch is oriented toward the active site) but sensitivity to H2O2-dependent inactivation indistinguishable from W321F/R418N KatG at pH 5 (i.e., when the Arg switch is oriented away from the active site). These data suggest loss of the Arg switch (either by mutagenesis or conformationally due to environmental pH) results in a KatG that is substantially compromised in the sustained degradation of H2O2. This can be overcome provided that KatG retains its ability to utilize the proximal Trp as a site of protein-based oxidation and has a PxED available to repair protein oxidation events. However, if both the Arg switch and the proximal Trp are absent, rapid H2O2-dependent inactivation is observed, and PxEDs are unable to effectively intervene to preserve KatG’s catalase activity.

Enhanced Catalytic Oxidation Reactivity over Atomically Dispersed Pt/CeO2 Catalysts by CO Activation.

The elevation of the low-temperature oxidation activity for Pt/CeO2 catalysts is challenging to meet the increasingly stringent requirements for effectively eliminating carbon monoxide (CO) from automobile exhaust. Although reducing activation is a facile strategy for boosting reactivity, past research has mainly concentrated on applying H2 as the reductant, ignoring the reduction capabilities of CO itself, a prevalent component of automobile exhaust. Herein, atomically dispersed Pt/CeO2 was fabricated and activated by CO, which could lower the 90% conversion temperature (T90) by 256 °C and achieve a 20-fold higher CO consumption rate at 200 °C. The activated Pt/CeO2 catalysts showed exceptional catalytic oxidation activity and robust hydrothermal stability under the simulated working conditions for gasoline or diesel exhausts. Characterization results illustrated that the CO activation triggered the formation of a large portion of Pt0 terrace sites, acting as inherent active sites for CO oxidation. Besides, CO activation weakened the Pt-O-Ce bond strength to generate a surface oxygen vacancy (Vo). It served as the oxygen reservoir to store the dissociated oxygen and convert it into active dioxygen intermediates. Conversely, H2 activation failed to stimulate Vo, but triggered a deactivating transformation of the Pt nanocluster into inactive PtxOy in the presence of oxygen. The present work offers coherent insight into the upsurging effect of CO activation on Pt/CeO2, aiming to set up a valuable avenue in elevating the efficiency of eliminating CO, C3H6, and NH3 from automobile exhaust.

Surface anchoring requirements for vanadia clusters on titanium oxide surfaces and their impact on activity for oxidative dehydrogenation of ethanol

Titanium oxide site requirements for the anchoring of catalytically active forms of dispersed vanadia species are investigated. Using a series of oxygen-modified titanium nitride materials, we systematically modify the available vanadia-anchoring moieties on the titanium-bearing support surface. This strategy in turn results in a very narrow size distribution of well-dispersed vanadia clusters anchored on the support. This synthesis technique ensures that only highly dispersed vanadia is present on the catalyst surface even at nominal monolayer coverages. A deeper insight into the catalytic behavior for ethanol partial oxidation of the active vanadia species is obtained by comparing intrinsic kinetic and thermodynamic parameters of kinetically relevant reaction steps (heat of ethanol adsorption, hydrogen abstraction activation energy, and the energetics of catalyst reoxidation). It is found that these parameters are dependent on the relative amount of oxygen in the titanium-bearing support and the resulting distribution of vanadia species, which validates the premise of a potential participation of lattice oxygen atoms of the titania support into the catalytic activity of active vanadia species.

Photothermal CO2 conversion to ethanol through photothermal heterojunction-nanosheet arrays

Photothermal CO2 conversion to ethanol offers a sustainable solution for achieving net-zero carbon management. However, serious carrier recombination and high C-C coupling energy barrier cause poor performance in ethanol generation. Here, we report a Cu/Cu2Se-Cu2O heterojunction-nanosheet array, showcasing a good ethanol yield under visible–near-infrared light without external heating. The Z-scheme Cu2Se-Cu2O heterostructure provides spatially separated sites for CO2 reduction and water oxidation with boosted carrier transport efficiency. The microreactors induced by Cu2Se nanosheets improve the local concentration of intermediates (CH3* and CO*), thereby promoting C-C coupling process. Photothermal effect of Cu2Se nanosheets elevates system’s temperature to around 200 °C. Through synergizing electron and heat flows, we achieve an ethanol generation rate of 149.45 µmol g−1 h−1, with an electron selectivity of 48.75% and an apparent quantum yield of 0.286%. Our work can serve as inspiration for developing photothermal catalysts for CO2 conversion into multi-carbon chemicals using solar energy.

Redox-dependent plasticity of oxMIF facilitates its interaction with CD74 and therapeutic antibodies

MIF is a ubiquitous protein involved in proinflammatory processes, which undergoes an oxidation-driven conformational change to oxidized (ox)MIF. We demonstrate that hypochlorous acid, produced by neutrophil-released myeloperoxidase (MPO) under inflammatory conditions, effectively oxidizes MIF into the oxMIF isoform, which is specifically recognized by the anti-oxMIF therapeutic antibody, ON104. NMR investigation of MIF oxidized by the MPO system revealed increased flexibility throughout the MIF structure, including at several catalytic and allosteric sites. Mass spectrometry of MPO-oxMIF revealed methionines as the primary site of oxidation, whereas Pro2 and Tyr99/100 remained almost unmodified. ELISA, SPR and cell-based assays demonstrated that structural changes caused by MPO-driven oxidation promoted binding of oxMIF to its receptor, CD74, which does not occur with native MIF. These data reveal the environment and modifications that facilitate interactions between MIF and its pro-inflammatory receptor, and a route for therapeutic intervention targeting the oxMIF isoform.

Ultrasound-electrochemistry assisted liquid-phase co-exfoliation of phosphorene decorated by Au-Ag bimetallic nanoparticles as nanozyme for smartphone-based portable sensing of 4-nitrophenol.

The stability of black phosphorene (BP) and its preparation and modification for developing and applying devices have become a hot topic in the interdisciplinary field. We propose ultrasound-electrochemistry co-assisted liquid-phase exfoliation as an eco-friendly one-step method to prepare gold-silver bimetallic nanoparticles (Au-AgNPs)-decorated BP nanozyme for smartphone-based portable sensing of 4-nitrophenol (4-NP) in different water sources. The structure, morphology, composition, and properties of Au-AgNPs-BP nanozyme are characterized by multiple instrumental analyses. Bimetallic salts are induced to efficiently occupy oxidative sites of BP to form highly stable Au-AgNPs-BP nanozyme and guarantee the integrity of the lamellar BP. The electrochemistry shortens the exfoliation time of the BP nanosheet and contributes to the loading efficiency of bimetallic nanoparticles on the BP nanosheet. Au-AgNPs-BP-modified screen-printed carbon electrode coupled with palm-sized smartphone-controlled wireless electrochemical analyzer as a portable wireless intelligent sensing platform was applied to the determination of 4-NP in a linear range of 0.6-10 μM with a limit of detection of 63 nM. It enables on-site determination of 4-NP content in lake water, river water, and irrigation ditch water. This work will provide a reference for an eco-friendly one-step preparation of bimetallic nanoparticle-decorated graphene-like materials as nanozymes and their smartphone-based portable sensing application outdoors.

Enhanced sensing performance of flexible non-enzymatic electrochemical glucose sensors using hollow Fe3O4 nanospheres of controllable morphologies

Rapid and accurate monitoring of glucose concentration is of great significance in clinical diagnosis and treatment of diabetes and hence, it is necessary to develop glucose sensors of superior electro-catalytic capacity. Most literature utilize synergistic effect of nanocomposites to enhance glucose sensing performance, whereas it suffers from crucial restriction in physical and chemical characteristics of each constituents. Morphology of nanostructures significantly affects the electro-catalytic capacity, thus it is a novel route to improve glucose sensing performance to adjust morphology of nanostructures. Herein, we presented highly sensitive non-enzymatic electrochemical sensors for rapid and accurate glucose analysis with hollow Fe3O4 nanospheres (Fe3O4NSs) of controllable morphologies decorated on flexible fibers. The morphologies of the Fe3O4NSs were evaluated with quantitative parameters like diameter, roundness, roughness, skewness, and kurtosis acquired from SEM images and image processing algorithms, and their effect on the interfacial characteristics and the electro-catalytic capacity of the glucose sensors was investigated. Owing to the unique spherical nanostructures and superior catalysis, the Fe3O4NSs exhibit desirable solid/liquid interface for mass diffusion and abundant active sites for sufficient oxidation of glucose. Moreover, much rounder and rougher Fe3O4NSs of near Gaussian surface are readily produced at a higher Fe3+ concentration and result in favorable sensing performance. Accordingly, the optimal glucose sensor shows sensitivities of 96.1 ± 5.4 μA mM−1 cm−2 and 38.2 ± 2.2 μA mM−1 cm−2 over a preferable range of 0–18.0 mM, and a lower detection limit of 19.2 μM. Besides, the glucose sensors remain acceptable response after continuous testing for 20 times and repetitive bending for 50 times, and display superior selectivity to glucose and accurate analysis to practical samples. It is a facile and effective methodology to regulate the morphologies of the Fe3O4NSs for enhanced electro-catalytic capacity of glucose sensors.

Rich Sulfur Vacancies and Reduced Schottky Barrier Height Synergistically Enable Au/ZnIn2S4 with Enhanced Photocatalytic CO2 Reduction into CO.

Constructing the plasmonic metal/semiconductor heterostructure with a suitable Schottky barrier height (SBH) and the sufficiently reliable active sites is of importance to achieve highly efficient and selective photocatalytic CO2 reduction into hydrocarbon fuels. Herein, we report Au/sulfur vacancy-rich ZnIn2S4 (Au/VSR-ZIS) hierarchical photocatalysts, fabricated via in situ photodepositing Au nanoparticles (NPs) onto the nanosheet self-assembled ZnIn2S4 (ZIS) micrometer flowers (MFs) with rich sulfur vacancies (VS). Density functional theory (DFT) calculations confirm that for the Au/VSR-ZIS system, the Au NPs serve as the reaction sites for H2O oxidation, and the VSR-ZIS MFs serve as those for CO2 reduction. The rich VS in the Au/VSR-ZIS hybrid can reduce its SBH so as to boost more hot electrons in the Au NPs across its Schottky barrier and then inject into the conduction band (CB) of the VSR-ZIS MFs. In addition, VS can also act as the electron sink to trap the photogenerated electrons, retarding the recombination of photogenerated carriers. The two merits effectively enhance the photogenerated electron density in the surface of VSR-ZIS MFs, availing CO2 photoreduction. In addition, the introduction of rich VS in the Au/VSR-ZIS hybrid can offer more active sites, benefiting the CO2 adsorption and accelerating the desorption of CO* from the surface of the photocatalyst. Therefore, under visible light illumination with no sacrificial reagent, the optimum photocatalyst (Au/VSR-ZIS-0.4) presents the enhanced and selective CO2 photoreduction into CO (8.15 μmol g-1h-1 and near 100%), which are superior to those of most of ZIS-based and plasmon-based photocatalysts. The photocatalytic activity is about 40.0-fold as high as that of the Vs-poor-ZIS (VSP-ZIS) MFs. This work contributes a viable strategy for designing highly efficient plasmonic photocatalysts by using the synergism of the anion vacancies and the optimized SBH induced by them.

New insights and reaction mechanisms in the design of catalysts for the synergistic removal of NOx and VOCs from coke oven flue gas: Dual regulation of oxidative properties and acidic sites

The acid and redox sites of the MnCo catalysts are simultaneously fine-tuned by the addition of V. A dual-function catalyst, designated as V0.5Mn5Co5, has been constructed for the synergistic removal of NOx and volatile organic compounds under coke-oven flue gas conditions, which exhibits > 95 % NOx conversion and > 80 % N2 selectivity at 180–300 °C. Meanwhile, it removes 70 % of ethylene at 240 °C. Besides it has excellent sulfur and water resistance. The characterization results indicate that this acid-redox dual sites modulation strategy appropriately weakens the oxidation capacity of the catalysts while increasing the surface acidity of the catalysts. The catalyst mainly performs SCR reaction through the E-R mechanism, and N2O is generated through the transition dehydrogenation of NH3 and NSCR reaction. Ethylene is first adsorbed on the catalyst surface then oxidized to form carbonate species, and finally decomposed to CO2. Ethylene oxidation follows the MvK mechanism. There is a competitive adsorption between NH3 and C2H4, and a mutual inhibition between the SCR reaction and the ethylene oxidation reaction. V0.5Mn5Co5 exhibits excellent synergistic removal of NOx and VOCs in coke oven flue gas compared with commercial VWTi catalysts, which indicates great promise for industrial application.

Barium titanate photocatalysts with silver-manganese dual cocatalyst for carbon dioxide reduction with water.

Titanate photocatalysts with suitable cocatalysts are promising candidates for photocatalytic CO2 reduction, with the use of water as an electron donor. Here, several barium titanates with various compositions were examined, and BaTi4O9 (BT4) was found to be the best photocatalyst with the assistance of an Ag cocatalyst for photocatalytic CO2 reduction to form CO. The photocatalytic activity was further enhanced by the use of MnOx as an additional cocatalyst to construct an Ag-MnOx/BT4 photocatalyst, where Ag and MnOx were selectively deposited at different facets on BT4 crystal and functioned as active sites for CO2 reduction and water oxidation, respectively. As for the oxidative products from water, molecular oxygen (O2) and hydrogen peroxide (H2O2) were obtained.