The remarkable performance of a single iridium atom supported on hematite for methane activation: a density functional theory study

Methane is the major component of natural gas, and it significantly contributes to global warming. In this study, we investigated methane activation on the α-Fe₂O₃(110) surface and M/α-Fe₂O₃(110) surfaces (M = Ag, Ir, Cu, or Co) using the density-functional theory (DFT) + U method. Our study shows that the Ir/α-Fe₂O₃(110) surface is a more effective catalyst for C–H bond activation than other catalyst surfaces. We have applied electron density difference (EDD), density of states (DOS), and Bader charge calculations to confirm the cooperative CH⋯O and agostic interactions between CH₄ and the Ir/α-Fe₂O₃(110) surface. To further modify the reactivity of the Ir/α-Fe₂O₃(110) surface towards methane activation, we conducted a study of the effect of oxygen vacancy (O_V) on C–H activation and CH₄ dehydrogenation. In the comparison of pristine α-Fe₂O₃(110), Ir/α-Fe₂O₃(110), and Ir/α-Fe₂O₃(110)–O_V surfaces, the Ir/α-Fe₂O₃(110)–O_V surface is the best in terms of CH₄ adsorption energy and C–H bond elongation, whereas the Ir/α-Fe₂O₃(110) surface catalyst has the lowest C–H bond activation barrier for the CH₄ molecule. The calculations indicate that the Ir/α-Fe₂O₃(110)–O_V surface could be a candidate catalyst for CH₄ dehydrogenation reactions.

The Fe₂O₃(110)–O_V surface is the best in terms of CH₄ adsorption energy and C–H bond elongation. Therfore, the Ir/α-Fe₂O₃(110)–O_V surface could be a candidate catalyst for CH₄ dehydrogenation reaction.     

A novel superparamagnetic powerful guanidine-functionalized γ-Fe2O3 based sulfonic acid recyclable and efficient heterogeneous catalyst for microwave-assisted rapid synthesis of quinazolin-4(3H)-one derivatives in Green media

The novel organic–inorganic nanohybrid superparamagnetic (γ-Fe₂O₃@CPTMS–guanidine@SO₃H) nanocatalyst modified with sulfonic acid represents an efficient and green catalyst for the one-pot synthesis of quinazolin-4(3H)-one derivatives via three-component condensation reaction between anthranilic acid, acetic anhydride and different amines under microwave irradiation and solvent-free conditions (4a–q). XRD, FT-IR, FE-SEM, TGA, VSM and EDX were used to characterize this new magnetic organocatalyst. Outstanding performance, short response time (15–30 min), simple operation, easy work-up procedure, and avoidance of toxic catalysts can be regarded as its significant advantages. Moreover, it can be easily separated from the reaction solution through magnetic decantation using an external magnet, and recycled at least six times without notable reduction in its activity.

A novel organic–inorganic nanohybrid superparamagnetic nanocatalyst (γ-Fe₂O₃@CPTMS–guanidine@SO₃H) represents an efficient and green catalyst for the one-pot synthesis of quinazolin-4(3H)-one derivatives via a three-component condensation reaction.     

Highly efficient reduction of 4-nitrophenolate to 4-aminophenolate by Au/γ-Fe2O3@HAP magnetic composites

In this article, the catalyst Au/γ-Fe₂O₃@hydroxyapatite (Au/γ-Fe₂O₃@HAP) consisting of Au nanoparticles supported on the core–shell structure γ-Fe₂O₃@HAP was prepared through a deposition–precipitation method. The catalyst was characterized by transmission electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, N₂ adsorption–desorption and atomic absorption spectrometry. The as-prepared Au/γ-Fe₂O₃@HAP exhibited excellent performance for the reduction of 4-nitrophenolate (4-NP) to 4-aminophenolate (4-AP) in the presence of NaBH₄ at room temperature. Thermodynamic and kinetic data on the reduction of 4-NP to 4-AP catalyzed by the as-prepared catalyst were studied. The as-prepared catalyst could be easily separated by a magnet and recycled 6 times with over 92% conversion of 4-NP to 4-AP. In addition, the as-prepared catalyst showed excellent catalytic performance on other nitrophenolates. The TOF value of this work on the reduction of 4-NP to 4-AP was 241.3 h⁻¹. Au/γ-Fe₂O₃@HAP might have a promising potential application on the production of 4-AP and its derivatives.

In this article, the catalyst Au/γ-Fe₂O₃@hydroxyapatite (Au/γ-Fe₂O₃@HAP) consisting of Au nanoparticles supported on the core–shell structure γ-Fe₂O₃@HAP was prepared through a deposition–precipitation method.     

Light and magnetism dual-gated photoinduced electron transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization

A novel raspberry-like γ-Fe₂O₃@carbon dot (CD) nanocatalyst was prepared and applied for photoinduced electron transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization. The nanocatalyst was found to be an efficient photocatalyst in visible light-regulated PET-RAFT polymerization owing to the oxidative quenching mechanism between the photoexcited γ-Fe₂O₃@CDs and the RAFT agent in the PET process. Notably, polymerization can be reversibly ceased in the absence of light or under an external magnetic field. The superparamagnetic nature and high saturation magnetization value (∼30.4 emu g⁻¹) of the nanocatalyst contribute to convenient recycling of the nanocatalyst after polymerization. The PET-RAFT polymerization with the nanocatalyst before and after recycling was investigated, which displayed all the characteristics of controlled/living polymerization systems.

PET-RAFT polymerization can be reversibly ceased in the absence of light or under an external magnetic field with a novel raspberry-like γ-Fe₂O₃@CD nanocatalyst.     

Dendritic structured palladium complexes: magnetically retrievable,highly efficient heterogeneous nanocatalyst for Suzuki and Heck cross-coupling reactions

The recyclable nanomagnetic Pd-complex PAMAM G₀-Pd@γ-Fe₂O₃ is reported for catalytic C–C cross-coupling reactions of challenging substrates. Mainly, a great variety of aryl chlorides can be used as substrates for Suzuki–Miyaura and Mizoroki–Heck reactions under mild reaction conditions (60–90 °C) and low catalyst loading (<1 mol% Pd) in aqueous media. The presence of numerous polar groups in the polymer matrix increases the solubility of the catalyst in water, thus facilitating its operation in aqueous environments. The immobilization of the catalyst on the surface of a magnetic platform allows its effective recovery and reuse without significant loss of catalytic activity for at least six cycles with total leaching of <1% palladium metal, meeting the requirements for acceptable metal residues in the pharmaceutical industry.

The recyclable nanomagnetic Pd-complex PAMAM G₀-Pd@γ-Fe₂O₃ is reported for catalytic C–C cross-coupling reactions of challenging substrates.     

α-Fe2O3 hollow meso–microspheres grown on graphene sheets function as a promising counter electrode in dye-sensitized solar cells

Although nanoparticles, nanorods, and nanosheets of α-Fe₂O₃ on graphene sheets have been synthesized, it remains a challenge to grow 3D α-Fe₂O₃ nanomaterials with more sophisticated compositions and structures on the graphene sheets. Herein, we demonstrate a facile solvothermal route under controlled conditions to successfully fabricate 3D α-Fe₂O₃ hollow meso–microspheres on the graphene sheets (α-Fe₂O₃/RGO HMM). Attributed to the combination of the catalytic features of α-Fe₂O₃ hollow meso–microspheres and the high conductivity of graphene, α-Fe₂O₃/RGO HMM exhibited promising electrocatalytic performance as a counter electrode in dye-sensitized solar cells (DSSCs). The DSSCs fabricated with α-Fe₂O₃ HMM displayed high power conversion efficiency of 7.28%, which is comparable with that of Pt (7.71%).

Although nanoparticles, nanorods, and nanosheets of α-Fe₂O₃ on graphene sheets have been synthesized, it remains a challenge to grow 3D α-Fe₂O₃ nanomaterials with more sophisticated compositions and structures on the graphene sheets.     

Crystal growth control of rod-shaped ε-Fe2O3 nanocrystals

Herein we report crystal growth control of rod-shaped ε-Fe₂O₃ nanocrystals by developing a synthesis based on the sol–gel technique using β-FeO(OH) as a seed in the presence of a barium cation. ε-Fe₂O₃ nanocrystals are obtained over a wide calcination temperature range between 800 °C and 1000 °C. A low calcination temperature (800 °C) provides an almost cubic rectangular-shaped ε-Fe₂O₃ nanocrystal with an aspect ratio of 1.4, whereas a high calcination temperature (1000 °C) provides an elongated rod-shaped ε-Fe₂O₃ nanocrystal with an aspect ratio of 3.3. Such systematic anisotropic growth of ε-Fe₂O₃ is achieved due to the wide calcination temperature in the presence of barium cations. The surface energy and the anisotropic adsorption of barium on the surface of ε-Fe₂O₃ can explain the anisotropic crystal growth of rod-shaped ε-Fe₂O₃ along the crystallographic a-axis. The present work may provide important knowledge about how to control the anisotropic crystal shape of nanomaterials.

Crystal growth control of rod-shaped ε-Fe₂O₃ nanocrystals is achieved by a synthesis based on the sol–gel technique.     

Novel magnetic g-C3N4/α-Fe2O3/Fe3O4 composite for the very effective visible-light-Fenton degradation of Orange II

A novel magnetic heterogeneous g-C₃N₄/α-Fe₂O₃/Fe₃O₄ catalyst was successfully synthesized through a simple hydrothermal method. The structure, morphology, and optical properties of the catalyst were characterized. The photocatalytic activity of the heterogeneous g-C₃N₄/α-Fe₂O₃/Fe₃O₄ catalyst for the photo-Fenton degradation of Orange II in the presence of H₂O₂ irradiated with visible light (λ > 420 nm) at neutral pH was evaluated. The g-C₃N₄/α-Fe₂O₃/Fe₃O₄ photocatalyst was found to be an excellent catalyst for the degradation of Orange II and offers great advantages over the traditional Fenton system (Fe(ii/iii)/H₂O₂). The results indicated that successfully combining monodispersed Fe₃O₄ nanoparticles and g-C₃N₄/α-Fe₂O₃ enhanced light harvesting, retarded photogenerated electron–hole recombination, and significantly enhanced the photocatalytic activity of the system. The g-C₃N₄/α-Fe₂O₃/Fe₃O₄ (30%) sample gave the highest degradation rate constant, 0.091 min⁻¹, which was almost 4.01 times higher than the degradation rate constant for α-Fe₂O₃ and 2.65 times higher than the degradation rate constant for g-C₃N₄/α-Fe₂O₃ under the same conditions. A reasonable mechanism for catalysis by the g-C₃N₄/α-Fe₂O₃/Fe₃O₄ composite was developed. The g-C₃N₄/α-Fe₂O₃/Fe₃O₄ composite was found to be stable and recyclable, meaning it has great potential for use as a photo-Fenton catalyst for effectively degrading organic pollutants in wastewater.

A novel magnetic heterogeneous g-C₃N₄/α-Fe₂O₃/Fe₃O₄ catalyst was firstly synthesized and exhibited very effective visible-light-Fenton degradation of Orange II at neutral pH.     

Halide-free neodymium phosphate based catalyst for highly cis-1,4 selective polymerization of dienes

Neodymium-based Ziegler–Natta type catalytic systems are known to produce polydienes with high cis-1,4 content. It is generally believed that in Ziegler–Natta catalytic systems, a halide or pseudohalide, whether in the catalyst itself or a separate source, is required for the success of the polymerization. In this work, we have synthesized an unusual halide-free neodymium diethyl phosphate catalyst for diene polymerization. This neodymium complex combined with triisobutylaluminum (TIBA), formed a binary catalytic system and was used to polymerize β-myrcene. The catalytic system displays high stereospecificity and produces poly(β-myrcene) with 96% cis-1,4 content and a relatively narrow molecular weight distribution (M_w/M_n = 1.80). Also, kinetic studies indicated the catalytic system gives a pseudo-living polymerization. The block copolymer poly(β-myrcene)-b-poly(isoprene) was successfully synthesized by sequential monomer addition, further demonstrating the pseudo-living nature of polymerization with the neodymium diethyl phosphate catalyst.

[Nd(μ-DEP)₃]_x/TIBA stereospecifically polymerizes myrcene in a pseudo-living Ziegler–Natta like catalytic system despite the absence of a halide.     

Magnetic hyperthermia with ε-Fe2O3 nanoparticles

Biocompatibility restrictions have limited the use of magnetic nanoparticles for magnetic hyperthermia therapy to iron oxides, namely magnetite (Fe₃O₄) and maghemite (γ-Fe₂O₃). However, there is yet another magnetic iron oxide phase that has not been considered so far, in spite of its unique magnetic properties: ε-Fe₂O₃. Indeed, whereas Fe₃O₄ and γ-Fe₂O₃ have a relatively low magnetic coercivity, ε-Fe₂O₃ exhibits a giant coercivity. In this report, the heating power of ε-Fe₂O₃ nanoparticles in comparison with γ-Fe₂O₃ nanoparticles of similar size (∼20 nm) was measured in a wide range of field frequencies and amplitudes, in uncoated and polymer-coated samples. It was found that ε-Fe₂O₃ nanoparticles primarily heat in the low-frequency regime (20–100 kHz) in media whose viscosity is similar to that of cell cytoplasm. In contrast, γ-Fe₂O₃ nanoparticles heat more effectively in the high frequency range (400–900 kHz). Cell culture experiments exhibited no toxicity in a wide range of nanoparticle concentrations and a high internalization rate. In conclusion, the performance of ε-Fe₂O₃ nanoparticles is slightly inferior to that of γ-Fe₂O₃ nanoparticles in human magnetic hyperthermia applications. However, these ε-Fe₂O₃ nanoparticles open the way for switchable magnetic heating owing to their distinct response to frequency.

ε-Fe₂O₃ is a magnetic iron(iii) oxide with a giant coercivity. Its potential in hyperthermia applications has been evaluated in comparison with γ-Fe₂O₃ over a wide range of field frequencies and amplitudes.     

Enhancing the light olefin selectivity of an iron-based Fischer–Tropsch synthesis catalyst by modification with CTAB

The effects of the surfactant hexadecyltrimethylammonium bromide (CTAB) on the catalytic performance of a manganese-promoted iron (FeMn) catalyst for the Fischer–Tropsch to olefin (FTO) reaction were investigated. The use of the CTAB-assisted FeMn catalyst resulted in the production of light olefin (C_2–4 ) selectivity of up to 55.45% with a ratio of olefin to paraffin among the C₂–C₄ hydrocarbons as high as 7.75 under industrially relevant conditions (320 °C, 1.0 MPa, H₂/CO ratio of 1.5 (v/v), GHSV = 4200 h⁻¹). The characterization results indicate that CTAB has a great influence on the structure, composition, chemical state, and catalytic performance of the iron-based catalyst. Most interestingly, a greater amount of Mn promoter was found to be dispersed on the surface of α-Fe₂O₃, rather than being dissolved into the α-Fe₂O₃ lattice when CTAB was employed, which contributed towards enhancing the promotional effects of the Mn promoter, leading to the formation of certain surface-specific activity sites.

The effects of the surfactant hexadecyltrimethylammonium bromide (CTAB) on the catalytic performance of a manganese-promoted iron (FeMn) catalyst for the Fischer–Tropsch to olefin (FTO) reaction were investigated.     

Synergistic effect of modified pore and heterojunction of MOF-derived α-Fe2O3/ZnO for superior photocatalytic degradation of methylene blue

Mesoporous heterojunction MOF-derived α-Fe₂O₃/ZnO composites were prepared by a simple calcination of α-Fe₂O₃/ZIF-8 as a sacrificial template. The optical properties confirm that coupling of both the modified pore and the n–n heterojunction effectively reduces the possibility of photoinduced charge carrier recombination under irradiation. The mesoporous Fe(25)ZnO with 25% loading of α-Fe₂O₃ exhibited the best performance in MB degradation, up to ∼100% after 150 minutes irradiation, higher than that of pristine ZnO and α-Fe₂O₃. Furthermore, after three cycles reusability, mesoporous Fe(25)ZnO still showed an excellent stability performance of up to 95.42% for degradation of MB. The proposed photocatalytic mechanism of mesoporous Fe(25)ZnO for the degradation of MB corresponds to the n–n heterojunction system. This study provides a valuable reference for preparing mesoporous MOF-derived metal oxides with an n–n heterojunction system to enhance MB photodegradation.

Mesoporous heterojunction MOF-derived α-Fe₂O₃/ZnO composites were prepared by a simple calcination of α-Fe₂O₃/ZIF-8 as a sacrificial template.     

The production of an efficient visible light photocatalyst for CO oxidation through the surface plasmonic effect of Ag nanoparticles on SiO2@α-Fe2O3 nanocomposites

A process for the photo deposition of noble Ag nanoparticles on a core–shell structure of SiO₂@α-Fe₂O₃ nanocomposite spheres was performed to produce a CO photo oxidation catalyst. The structural analyses were carried out for samples produced using different Ag metal nanoparticle weight percentages on SiO₂@α-Fe₂O₃ nanocomposite spheres by X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), UV-vis spectroscopy, Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR). A computational study was also performed to confirm the existence of the synergic effect of surface plasmon resonance (SPR) for different weight percentages of Ag on the SiO₂@α-Fe₂O₃ nanocomposites. The mechanism for CO oxidation on the catalyst was explored using diffuse reflectance infrared Fourier transform spectroscopy (DRFIT). The CO oxidation results for the Ag (2 wt%)-SiO₂@α-Fe₂O₃ nanocomposite spheres showed 48% higher photocatalytic activity than α-Fe₂O₃ and SiO₂@α-Fe₂O₃ at stable temperature.

We present a systematic investigation of CO oxidation and surface plasmon resonance on SiO₂@α-Fe₂O₃ nanocomposite spheres with different weight percentages of Ag nanoparticles.     

Preparation of Ag3PO4/α-Fe2O3 hybrid powders and their visible light catalytic performances

The inefficiency of conventional photocatalytic treatment for removing rhodamine B is posing potential risks to ecological environments. Here, we construct a highly efficient photocatalyst consisting of Ag₃PO₄ and α-Fe₂O₃ hybrid powders for the treatment of rhodamine B. Ag₃PO₄ nanoparticles (nanoparticles, about 50 nm) are uniformly dispersed on the surface of α-Fe₂O₃ microcrystals (hexagonal sheet, about 1.5 μm). The Ag₃PO₄-deposited uniformity on the α-Fe₂O₃ surface first increased, then decreased on increasing the hybrid ratio of Ag₃PO₄ to α-Fe₂O₃. When the hybrid ratio of Ag₃PO₄ to α-Fe₂O₃ is 1 : 2, the distribution of Ag₃PO₄ particles on the sheet α-Fe₂O₃ is more uniform with excellent Ag₃PO₄/α-Fe₂O₃ interface performance. The catalytic degradation efficiency of hybrids with the introduction of Ag₃PO₄ nanoparticles on the α-Fe₂O₃ surface reached 95%. More importantly, the hybrid material exhibits superior photocatalytic stability. Ag₃PO₄/α-Fe₂O₃ hybrids have good reusability, and the photocatalytic efficiency could still reach 72% after four reuses. The excellent photocatalytic activity of the as-prepared hybrids can be attributed to the heterostructure between Ag₃PO₄ and α-Fe₂O_3, which can effectively inhibit the photoelectron–hole recombination and broaden the visible light response range.

We construct a highly efficient photocatalyst consisting of Ag₃PO₄ and α-Fe₂O₃ hybrid powders for the treatment of rhodamine B. The catalytic degradation efficiency reached 95% after 10 min.     

Tandem imine formation via auto-hydrogen transfer from alcohols to nitro compounds catalyzed by a nanomagnetically recyclable copper catalyst under solvent-free conditions

A direct imination reaction was developed by tandem reaction of alcohols and nitro compounds in the presence of Cu-isatin Schiff base-γ-Fe₂O₃ as a nanomagnetically recyclable catalyst under solvent-free conditions. By this method, various imines were prepared in good to high yields from one-pot reaction of various alcohols (primary aromatic and aliphatic) and nitro compounds (aromatic and aliphatic) via an auto-hydrogen transfer reaction. Use of an inexpensive and easily reusable catalyst, without requiring any additives or excess amounts of benzyl alcohol as the reaction solvent are the other advantages of this method. This catalytic system has the merits of cost effectiveness, environmental benignity, excellent recyclability and good reproducibility.

A direct imination reaction was developed by tandem reaction of alcohols and nitro compounds in the presence of Cu-isatin Schiff base-γ-Fe₂O₃ as a nanomagnetically recyclable catalyst.     

Synthesis and characterization of an α-Fe2O3/ZnTe heterostructure for photocatalytic degradation of Congo red,methyl orange and methylene blue

The leading challenge towards environmental protection is untreated textile dyes. Tailoring photocatalytic materials is one of the sustainable remediation strategies for dye treatment. Hematite (α-Fe₂O₃), due to its favorable visible light active band gap (i.e. 2.1 eV), has turned out to be a robust material of interest. However, impoverished photocatalytic efficiency of α-Fe₂O₃ is ascribable to the short life span of the charge carriers. Consequently, the former synthesized heterostructures possess low degradation efficiency. The aim of the proposed endeavor is the synthesis of a novel zinc telluride-modified hematite (α-Fe₂O₃/ZnTe) heterostructure, its characterization and demonstration of its enhanced photocatalytic response. The promising heterostructure as well as bare photocatalysts were synthesized via a hydrothermal approach. All photocatalysts were characterized by the X-ray diffraction technique (XRD), scanning electron microscopy (SEM), and electron diffraction spectroscopy (EDX). Moreover, the selectivity and activity of the photocatalyst are closely related to the alignment of its band energy levels, which were estimated by UV-Vis diffuse reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS). Nanomaterials, specifically α-Fe₂O₃ and α-Fe₂O₃/ZnTe, were used for the degradation of Congo red (97.9%), methyl orange (84%) and methylene blue (73%) under light irradiation (>200 nm) for 60 min. The results suggested that with the aforementioned optimized fabricated heterostructure, the degradation efficiency was improved in comparison to bare hematite (α-Fe₂O₃). The key rationale towards such improved photocatalytic response is the establishment of a type-II configuration in the α-Fe₂O₃/ZnTe heterostructure.

Effective generation and transportation of electron–hole pairs in the presence of light leads to efficient degradation of textile pollutants over an α-Fe₂O₃/ZnTe nanocomposite compared to the individual components.     

Mesoporous anodic α-Fe2O3 interferometer for organic vapor sensing application

In this work, we reported the utilization of mesoporous α-Fe₂O₃ films as optical sensors for detecting organic vapors. The mesoporous α-Fe₂O₃ thin films, which exhibited obvious Fabry–Perot interference fringes in the reflectance spectrum, were successfully fabricated through electrochemical anodization of Fe foils. Through monitoring the optical thickness of the interference fringes, three typical organic species with different vapor pressures and polarities (hexane, acetone and isopropanol) were applied as probes to evaluate the sensitivity of the α-Fe₂O₃ based interferometric sensor. The experiment results showed that the as-synthesized mesoporous α-Fe₂O₃ interferometer displayed high reversibility and stability for the three organic vapors, and were especially sensitive to isopropanol, with a detection limit of about 65 ppmv. Moreover, the photocatalytic properties of α-Fe₂O₃ under visible light are beneficial for degradation of dodecane vapor residues in the nano-pores and refreshment of the sensor, demonstrating good self-cleaning properties of the α-Fe₂O₃-based interferometric sensor.

Mesoporous α-Fe₂O₃ interferometers with well-resolved optical fringes can display high sensitivity to organic vapors.     

Environment-friendly magnetic Fe–Ce–W catalyst for the selective catalytic reduction of NOx with NH3: influence of citric acid content on its activity-structure relationship

The influence of the citric acid content on the structural and redox properties of a magnetic iron–cerium–tungsten mixed oxide catalyst prepared through a microwave-assisted citric acid sol–gel method is investigated via TG–DTG–DSC, XRD, N₂ adsorption–desorption, XPS, H₂-TPR and NH₃-TPD. Additionally, the NH₃-SCR activity of the magnetic FeCeW-m (m = 0.25, 0.5 and 1.0) catalysts are also studied. The results indicate that an increase in citric acid content strengthens the sol–gel reaction between citric acid and metal ions and promotes the formation of the γ-Fe₂O₃ crystallite not α-Fe₂O₃. Meanwhile, it decreases the BET surface area and pore volume of the catalyst. Furthermore, the surface concentration of iron species on the catalyst is enhanced when the molar ratio of citric acid/(Fe + Ce + W) increases from 0.25 to 1.0, but its surface absorbed oxygen and total oxygen concentration decrease. The magnetic FeCeW-0.5 catalyst shows the best reducibility at temperatures below 790 °C. The increase in the citric acid content inhibits the formation of acid sites in the catalyst, thus the magnetic FeCeW-0.25 catalyst possesses the most Lewis acid sites and Brønsted acid sites among the catalysts. The enhancement in citric acid content is beneficial to improve the SCR reaction rates normalized by the surface area of the catalyst. This catalyst exhibits high anti-SO₂ and H₂O poisoning, and the molar ratio of citric acid/(Fe + Ce + W) affects the adsorption of NO_x species on its surface.

The enhancement of critic acid amount strengthened the sol–gel reaction between critic acid and metal ions, showed an important role on the structure properties of magnetic Fe–Ce–W mixed oxide catalyst, thereby affected its NH₃-SCR activity.     

Heterostructures of ε-Fe2O3 and α-Fe2O3: insights from density functional theory

Many materials used in energy devices or applications suffer from the problem of electron–hole pair recombination. One promising way to overcome this problem is the use of heterostructures in place of a single material. If an electric dipole forms at the interface, such a structure can lead to a more efficient electron–hole pair separation and thus prevent recombination. Here we model and study a heterostructure comprised of two polymorphs of Fe₂O₃. Each one of the two polymorphs, α-Fe₂O₃ and ε-Fe₂O₃, individually shows promise for applications in photoelectrochemical cells. The heterostructure of these two materials is modeled by means of density functional theory. We consider both ferromagnetic as well as anti-ferromagnetic couplings at the interface between the two systems. Both individual oxides are insulating in nature and have an anti-ferromagnetic spin arrangement in their ground state. The same properties are found also in their heterostructure. The highest occupied electronic orbitals of the combined system are localized at the interface between the two iron-oxides. The localization of charges at the interface is characterized by electrons residing close to the oxygen atoms of ε-Fe₂O₃ and electron–holes localized on the iron atoms of α-Fe₂O₃, just around the interface. The band alignment at the interface of the two oxides shows a type-III broken band-gap heterostructure. The band edges of α-Fe₂O₃ are higher in energy than those of ε-Fe₂O₃. This band alignment favours a spontaneous transfer of excited photo-electrons from the conduction band of α- to the conduction band of ε-Fe₂O₃. Similarly, photo-generated holes are transferred from the valence band of ε- to the valence band of α-Fe₂O₃. Thus, the interface favours a spontaneous separation of electrons and holes in space. The conduction band of ε-Fe₂O₃, lying close to the valence band of α-Fe₂O₃, can result in band-to-band tunneling of electrons which is a characteristic property of such type-III broken band-gap heterostructures and has potential applications in tunnel field-effect transistors.

Electron–hole pair recombination is reduced in heterostructures if used in devices in place of single material.     

Mn-based catalysts supported on γ-Al2O3, TiO2 and MCM-41: a comparison for low-temperature NO oxidation with low ratio of O3/NO

Mn-Based catalysts supported on γ-Al₂O₃, TiO₂ and MCM-41 synthesized by an impregnation method were compared to evaluate their NO catalytic oxidation performance with low ratio O₃/NO at low temperature (80–200 °C). Activity tests showed that the participation of O₃ remarkably promoted the NO oxidation. The catalytic oxidation performance of the three catalysts decreased in the following order: Mn/γ-Al₂O₃ > Mn/TiO₂ > Mn/MCM-41, indicating that Mn/γ-Al₂O₃ exhibited the best catalytic activity. In addition, there was a clear synergistic effect between Mn/γ-Al₂O₃ and O₃, followed by Mn/TiO₂ and O₃. The characterization results of XRD, EDS mapping, BET, H₂-TPR, XPS and TG showed that Mn/γ-Al₂O₃ had good manganese dispersion, excellent redox properties, appropriate amounts of coexisting Mn³⁺ and Mn⁴⁺ and abundant chemically adsorbed oxygen, which ensured its good performance. In situ DRIFTS demonstrated the NO adsorption performance on the catalyst surface. As revealed by in situ DRIFTS experiments, the chemically adsorbed oxygen, mainly from the decomposition of O₃, greatly promoted the NO adsorption and the formation of nitrates. The Mn-based catalysts showed stronger adsorption strength than the corresponding pure supports. Due to the abundant adsorption sites provided by pure γ-Al₂O₃, under the interaction of Mn and γ-Al₂O₃, the Mn/γ-Al₂O₃ catalyst exhibited the strongest NO adsorption performance among the three catalysts and produced lots of monodentate nitrates (–O–NO₂) and bidentate nitrates (–O₂NO), which were the vital intermediate species for NO₂ formation. Moreover, the NO–TPD studies also demonstrated that Mn/γ-Al₂O₃ showed the best NO desorption performance among the three catalysts. The good NO adsorption and desorption characteristics of Mn/γ-Al₂O₃ improved its high catalytic activity. In addition, the activity test results also suggested that Mn/γ-Al₂O₃ exhibited good SO₂ tolerance.

The Mn/γ-Al₂O₃ catalyst exhibited excellent performance for NO conversion in the presence of a low ratio of O₃/NO, which was due to the coexistence of Mn³⁺ and Mn⁴⁺ and abundant chemically adsorbed oxygen.