Magnetically Induced CO2 Methanation Using Exchange-Coupled Spinel Ferrites in Cuboctahedron-Shaped Nanocrystals

Magnetically induced catalysis can be promoted taking advantage of optimal heating properties from the magnetic nanoparticles to be employed. However, when unprotected, these heating agents that are usually air-sensitive, get sintered under the harsh catalytic conditions. In this context, we present, to the best of our knowledge, the first example of air-stable magnetic nanoparticles that: 1) show excellent performance as heating agents in the CO₂ methanation catalyzed by Ni/SiRAlOx, with CH₄ yields above 95 %, and 2) do not sinter under reaction conditions. To attain both characteristics we demonstrate, first the exchange-coupled magnetic approach as an alternative and effective way to tune the magnetic response and heating efficiency, and second, the chemical stability of cuboctahedron-shaped core–shell hard CoFe₂O₄–soft Fe₃O₄ nanoparticles.     

Magnetically Induced CO2 Methanation Using Exchange‐Coupled Spinel Ferrites in Cuboctahedron‐Shaped Nanocrystals

Magnetically induced catalysis can be promoted taking advantage of optimal heating properties from the magnetic nanoparticles to be employed. However, when unprotected, these heating agents that are usually air‐sensitive, get sintered under the harsh catalytic conditions. In this context, we present, to the best of our knowledge, the first example of air‐stable magnetic nanoparticles that: 1) show excellent performance as heating agents in the CO₂ methanation catalyzed by Ni/SiRAlOx, with CH₄ yields above 95 %, and 2) do not sinter under reaction conditions. To attain both characteristics we demonstrate, first the exchange‐coupled magnetic approach as an alternative and effective way to tune the magnetic response and heating efficiency, and second, the chemical stability of cuboctahedron‐shaped core–shell hard CoFe₂O₄–soft Fe₃O₄ nanoparticles.     

Copper-based metal-organic frameworks for electrochemical reduction of CO2

The electrochemical CO₂ reduction reaction (CO₂ER) is an emerging process that involves utilizing CO₂ to produce valuable chemicals and fuels by consuming excess electricity from renewable sources. Recently, Cu and Cu-based nanoparticles, as earth-abundant and economical metal sources, have been attracting significant interest. The chemical and physical properties of Cu-based nanoparticles are modified by different strategies, and CO₂ can be converted into multicarbon products. Among various Cu-based nanoparticles, Cu-based metal-organic frameworks (MOFs) are gaining increasing interest in the field of catalysis because of their textural, topological, and electrocatalytic properties. In this minireview, we summarized and highlighted the main achievements in the research on Cu-based MOFs and their advantages in the CO₂ER as electrocatalysts, supports, or precursors.     

Engineering Iron–Nickel Nanoparticles for Magnetically Induced CO2 Methanation in Continuous Flow

Induction heating of magnetic nanoparticles (NPs) is a method to activate heterogeneous catalytic reactions. It requires nano‐objects displaying high heating power and excellent catalytic activity. Here, using a surface engineering approach, bimetallic NPs are used for magnetically induced CO₂ methanation, acting both as heating agent and catalyst. The organometallic synthesis of Fe₃₀Ni₇₀ NPs displaying high heating powers at low magnetic field amplitudes is described. The NPs are active but only slightly selective for CH₄ after deposition on SiRAlOx owing to an iron‐rich shell (25 mL min^?1, 25 mT, 300 kHz, conversion 71 %, methane selectivity 65 %). Proper surface engineering consisting of depositing a thin Ni layer leads to Fe₃₀Ni₇₀@Ni NPs displaying a very high activity for CO₂ hydrogenation and a full selectivity. A quantitative yield in methane is obtained at low magnetic field and mild conditions (25 mL min^?1, 19 mT, 300 kHz, conversion 100 %, methane selectivity 100 %).     

Mesoporous silica-magnetite nanocomposite: facile synthesis route for application in hyperthermia

The synthesis of nanostructured magnetic materials has been intensively researched because of their large field of applications as magnetic carriers in drug targeting, hyperthermia in tumor treatment, among others. Much effort has been invested in magnetic nanoparticles for bioapplications. However, as these nanoparticles present high specific surface area, unprotected nanoparticles can easily form aggregates and react with oxygen in the air. They can also rapidly biodegrade when directly exposed to biological systems. In this context, we have explored the possibility of synthesizing a mesoporous SiO₂–Fe₃O₄ nanocomposite and its AC magnetic-field-induced heating properties. The magnetite nanocomposite was obtained by impregnation of an iron precursor into a silica framework. The proposed method involves the preparation of an iron oxide precursor in ethanol and the subsequent impregnation of SBA-15 mesoporous hexagonal silica. Iron oxide was formed inside the porous structure, thus producing the magnetic device. The nanocomposite was characterized by X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FTIR), N₂ adsorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Measurements of AC magnetic-field-induced heating properties of the obtained nanocomposite, both of the solid form and in aqueous solution, under different applied magnetic fields showed that it is suitable as a hyperthermia agent for biological applications.     

Engineering Iron–Nickel Nanoparticles for Magnetically Induced CO2 Methanation in Continuous Flow

Induction heating of magnetic nanoparticles (NPs) is a method to activate heterogeneous catalytic reactions. It requires nano-objects displaying high heating power and excellent catalytic activity. Here, using a surface engineering approach, bimetallic NPs are used for magnetically induced CO₂ methanation, acting both as heating agent and catalyst. The organometallic synthesis of Fe₃₀Ni₇₀ NPs displaying high heating powers at low magnetic field amplitudes is described. The NPs are active but only slightly selective for CH₄ after deposition on SiRAlOx owing to an iron-rich shell (25 mL min⁻¹, 25 mT, 300 kHz, conversion 71 %, methane selectivity 65 %). Proper surface engineering consisting of depositing a thin Ni layer leads to Fe₃₀Ni₇₀@Ni NPs displaying a very high activity for CO₂ hydrogenation and a full selectivity. A quantitative yield in methane is obtained at low magnetic field and mild conditions (25 mL min⁻¹, 19 mT, 300 kHz, conversion 100 %, methane selectivity 100 %).     

Electrodes modified with iron porphyrin and carbon nanotubes: application to CO2 reduction and mechanism of synergistic electrocatalysis

Electrodes modified with iron porphyrin and carbon nanotubes (FeP–CNTs) were prepared and used for CO₂ electroreduction. The adsorption of iron porphyrin onto the multiwalled carbon nanotubes was characterized by scanning electron microscopy and ultraviolet and visible spectroscopy. The electrochemical properties of the modified electrodes for CO₂ reduction were investigated by cyclic voltammetry and CO₂ electrolysis. The FeP–CNT electrodes exhibited less negative cathode potential and higher reaction rate than the electrodes modified only with iron porphyrin or carbon nanotubes. A mechanism of the synergistic catalysis was proposed and studied by electrochemical impedance spectroscopy and electron paramagnetic resonance. The direct electron transfer between iron porphyrin and carbon nanotubes was examined. The current study shed light on the mechanism of synergistic catalysis between CNTs and metalloporphyrin, and the iron porphyrin–CNT-modified electrodes showed great potential in the efficient CO₂ electroreduction.     

Biomineralization of Versatile CuS/Gd2O3 Hybrid Nanoparticles for MR Imaging and Antitumor Photothermal Chemotherapy

The versatile application of nanoparticles in integrating imaging and therapy has aroused extensive research interest in precision medicine. Of the various nanoparticles that have been studied, CuS has shown great potential in the construction of multifunctional agents, owing to its excellent photothermal heating properties. Herein, we report a facile one‐pot biomineralization approach for the preparation of versatile bovine‐serum‐albumin‐conjugated CuS/Gd₂O₃ hybrid nanoparticles (BSA?CuS/Gd₂O₃ HNPs), which simultaneously possessed strong longitudinal relaxivity, an outstanding photothermal effect, high drug‐loading capacity, and pH/temperature‐responsive drug release. The versatile nanoparticles were used for magnetic resonance imaging (MRI) and antitumor photothermal chemotherapy, both in vitro and in vivo. In vivo MRI showed that the BSA?CuS/Gd₂O₃ HNPs had a long circulation time and effective passive tumor‐uptake ability. More importantly, combined in vitro and in vivo therapy demonstrated that drug‐loaded BSA?CuS/Gd₂O₃ HNPs offered outstanding synergistic therapeutic efficacy for tumor inhibition.     

Iron Oxide Nanoparticles: Biosynthesis,Magnetic Behavior,Cytotoxic Effect

Iron oxide nanoparticles have attracted much attention because of their superparamagnetic properties and their potential applications in many fields such as magnetic storage devices, catalysis, sensors, superparamagnetic relaxometry (SPMR), and high-sensitivity biomolecule magnetic resonance imaging (MRI) for medical diagnosis and therapeutics. In this study, iron oxide nanoparticles (Fe₂O₃ NPs) have been synthesized using a taranjabin (camelthorn or persian manna) aqueous solution. The synthesized Fe₂O₃ NPs were identified through powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), field energy scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDX), vibrating-sample magnetometer (VSM) and Raman technics. The results show that the nanoparticles have a hexagonal structure with 20 to 60 nm in size. The cytotoxic effect of the synthesized nanoparticles has been tested upon application against lung cancer cell (A549) lines. It was found that there is no cytotoxic activity at lower concentrations of 200 μg/mL. The ability of the synthesized nanoparticles for lead removal in wastewaters was tested. Results show that highest concentration of adsorbent (50 mg/L) has maximum removal efficiency (96.73 %). So, synthesized Fe₂O₃ NPs can be a good candidate to use as heavy metals cleaner from contaminated waters.     

Smart hybrid magnetic self-assembled micelles and hollow capsules

Novel magnetic nano-composites are obtained by the self-assembly in water of polypeptide-based diblock copolymers polybutadiene-b-poly(glutamic acid) combined with hydrophobically modified γ-Fe₂O₃ nanoparticles. These hybrid supramolecular objects are either filled micelles (3-d) or hollow vesicles with a magnetic membrane (2-d), deformation of which under an applied magnetic field has been evidenced. These nanoparticles are also able to respond to stimuli such as pH and ionic strength due to the presence of the polypeptide block, thus forming what we called multi-responsive nanocapsules. These superparamagnetic hybrid self-assemblies offer attractive potentialities in biomedicine and biotechnology due to their dimensions (0.1–0.5 μm) small enough to stay for some time in the blood circulation, and due to the properties brought about by the iron oxide nanoparticles: possible manipulation by an external magnetic field gradient, local heating by a radio-frequency field for cancer radio-therapy, labeling of organs to enhance the contrast in Magnetic Resonance Imaging.     

An efficient Ag/MIL-100(Fe) catalyst for photothermal conversion of CO2 at ambient temperature

The conversion of CO₂ under mild condition is of great importance because these reactions involving CO₂ can not only produce value-added chemicals from abundant and inexpensive CO₂ feedstock but also close the carbon cycle. However, the chemical inertness of CO₂ requires the development of high-performance catalysts. Herein, Ag nanoparticles/MIL-100(Fe) composites were synthesized by simple impregnation-reduction method and employed as catalysts for the photothermal carboxylation of terminal alkynes with CO₂. MIL-100(Fe) could stabilize Ag nanoparticles and prevent them from aggregation during catalytic process. Taking the advantages of photothermal effects and catalytic activities of both Ag nanoparticles and MIL-100(Fe), various aromatic alkynes could be converted to corresponding carboxylic acid products (86%–92% yields) with 1 atm CO₂ at room temperature under visible light irradiation when using Ag nanoparticles/MIL-100(Fe) as photothermal catalysts. The catalysts also showed good recyclability with almost no loss of catalytic activity for three consecutive runs. More importantly, the catalytic performance of Ag nanoparticles/MIL-100(Fe) under visible light irradiation at room temperature was comparable to that upon heating, showing that the light source could replace conventional heating method to drive the reaction. This work provided a promising strategy of utilizing solar energy for achieving efficient CO₂ conversion to value-added chemicals under mild condition.     

Fibroporous polytetrafluoroethylene modified with iron nanoparticles: Structure and electronic and magnetic properties

A method for synthesizing iron-containing nanocomposite based on fibroporous polytetrafluoroethylene (PTFE) is described. Fibroporous PTFE obtained under the radiation of a CO₂ laser on block PTFE is modified in supercritical carbon dioxide (sc CO₂) to form micro- and nanoporous structures. Porous fluoropolymer is treated with a solution of bis(toluene)iron(0) obtained by metal-vapor synthesis (MVS). The composition and structure of iron-containing fluoropolymer is studied by transmission electron microscopy and X-ray photoelectron and Mössbauer spectroscopy. Fe nanoparticles with an average size of 9 nm, consisting of ～30% FeO and ～70% Fe³⁺, are registered in the sample. Fe⁰ nanoparticles are stabilized in fluoropolymer pores and are coated with nanoparticles of nonstoichiometric iron oxides that have superparamagnetic properties.     

Au-Fe3O4 heterostructures for catalytic,analytical, and biomedical applications

Au-Fe₃O₄ heterostructures including dumbbell-like dimer, core-shell structure, and flower-type nanoparticles (NPs), attract much attention due to their multiple modifiable surfaces and unique properties coming from either Au or Fe₃O₄ nanoparticles. This review focuses on the preparation methods and biomedical applications of these heterogenous NPs in the fields of catalysis, assay, multimodal imaging, and combination therapy.     

Molecular Solar Thermal Batteries through Combination of Magnetic Nanoparticle Catalysts and Tailored Norbornadiene Photoswitches

Cobalt catalysts are immobilized on the surface of iron oxide nanoparticles for the preparation of highly active quasi-homogeneous catalysts toward an efficient release of photochemically stored energy in norbornadiene-based photoswitches. The facile separation of the iron oxide nanoparticles through exploitation of the intrinsic magnetic properties of this material enables efficient cyclization of energy storage and release. Through the transition from cobalt (II) salphen to cobalt porphyrins, a 22.6-fold increase in the catalytic efficiency of the QC-NBD back-conversion is achieved, with an initial TOF of up to 3.64 s⁻¹ and excellent TON of over 3305. In addition, a series of novel “push–pull” functionalized norbornadiene derivatives is prepared, featuring excellent absorption properties with maxima up to 366 nm, quantum yields around 70 %, high energy storage capacities of up to 98.0 kJ mol⁻¹, and outstanding thermal stability with t_1/2 (25 °C) over 100 days. Finally, the energy storage potential of these molecular solar thermal (MOST) systems is harnessed in a heat release experiment. This demonstrates the potential of norbornadiene-based photoswitches in combination with efficient magnetic catalysts for the generation of environmentally benign process heat.     

Suppressive Strong Metal-Support Interactions on Ruthenium/TiO2 Promote Light-Driven Photothermal CO2 Reduction with Methane

Strong metal-support interactions (SMSI) have gained great attention in the heterogeneous catalysis field, but its negative role in regulating light-induced electron transfer is rarely explored. Herein, we describe how SMSI significantly restrains the activity of Ru/TiO₂ in light-driven CO₂ reduction by CH₄ due to the photo-induced transfer of electrons from TiO₂ to Ru. In contrast, on suppression of SMSI Ru/TiO₂−H₂ achieves a 46-fold CO₂ conversion rate compared to Ru/TiO₂. For Ru/TiO₂−H₂, a considerable number of photo-excited hot electrons from Ru nanoparticles (NPs) migrate to oxygen vacancies (OVs) and facilitate CO₂ activation under illumination, simultaneously rendering Ru^δ+ electron deficient and better able to accelerate CH₄ decomposition. Consequently, photothermal catalysis over Ru/TiO₂−H₂ lowers the activation energy and overcomes the limitations of a purely thermal system. This work offers a novel strategy for designing efficient photothermal catalysts by regulating two-phase interactions.     

Recent progress on two-dimensional materials confining single atoms for CO2 photoreduction

Photoreduction of CO₂ into value-added products offers a promising approach to overcome both climate change and energy crisis. However, low conversion efficiency, poor product selectivity, and unclear mechanism limit the further advancement of CO₂ photoreduction. The development of two-dimensional (2D) materials and construction of single atom sites are two frontier research fields in catalysis. Combining the advantages of 2D materials and single atom sites is expected to make a breakthrough in CO₂ photoreduction. In this review, we summarized the design and application, proposed challenges and opportunities, and laid a foundation for further research and application of 2D materials confining single atoms (SACs@2D) for CO₂ photoreduction.     

Ferrite nanoparticles (MFe2O4 NPs) as magnetically recoverable supports for catalysis in organic synthesis

Abstract

Heterogenization of organic and metallic catalysts with a solid support is an attractive and useful strategy to solve the separation and recovery problems of catalysts. During the last decade, magnetic nanoparticles (MNPs) in general ferrite nanoparticles (MFe₂O₄ NPs) have emerged as a highly efficient support for catalysis, due to their simple fabrication, modification, and large surface area ratio. In this paper, we provide an overview of the utilization of organic and metallic molecules immobilized on magnetic ferrite nanoparticles (MFe₂O₄ NPs) as attractive and efficient catalytic systems in wide variety of in organic reactions.     

Fundamental Aspects of Ceria Supported Au Catalysts Probed by In Situ/Operando Spectroscopy and TAP Reactor Studies

The discovery of the activity of dispersed gold nanoparticles three decades ago paved the way for a new era in catalysis. The unusual behavior of these catalysts sparked many questions about their working mechanism. In particular, Au/CeO₂ proved to be an efficient catalyst in several reactions such as CO oxidation, water gas shift, and CO₂ reduction. Here, by employing findings from operando X-ray absorption spectroscopy at the near and extended Au and Ce L_III energy edges, we focus on the fundamental aspects of highly active Au/CeO₂ catalysts, mainly in the CO oxidation for understanding their complex structure-reactivity relationship. These results were combined with findings from in situ diffuse reflectance FTIR and Raman spectroscopy, highlighting the changes of adlayer and ceria defects. For a comprehensive understanding, the spectroscopic findings will be supplemented by results of the dynamics of O₂ activation obtained from Temporal Analysis of Products (TAP). Merging these results illuminates the complex relationship among the oxidation state, size of the Au nanoparticles, the redox properties of CeO₂ support, and the dynamics of O₂ activation.     

Synergistic Porosity and Charge Effects in a Supramolecular Porphyrin Cage Promote Efficient Photocatalytic CO2 Reduction**

We present a supramolecular approach to catalyzing photochemical CO₂ reduction through second-sphere porosity and charge effects. An iron porphyrin box ( PB ) bearing 24 cationic groups, FePB-2(P) , was made via post-synthetic modification of an alkyne-functionalized supramolecular synthon. FePB-2(P) promotes the photochemical CO₂ reduction reaction (CO₂RR) with 97 % selectivity for CO product, achieving turnover numbers (TON) exceeding 7000 and initial turnover frequencies (TOF_max) reaching 1400 min⁻¹. The cooperativity between porosity and charge results in a 41-fold increase in activity relative to the parent Fe tetraphenylporphyrin ( FeTPP ) catalyst, which is far greater than analogs that augment catalysis through porosity ( FePB-3(N ), 4-fold increase) or charge (Fe p-tetramethylanilinium porphyrin ( Fe-p-TMA ), 6-fold increase) alone. This work establishes that synergistic pendants in the secondary coordination sphere can be leveraged as a design element to augment catalysis at primary active sites within confined spaces.     

Elemental Boron for Efficient Carbon Dioxide Reduction under Light Irradiation

The photoreduction of CO₂ is attractive for the production of renewable fuels and the mitigation of global warming. Herein, we report an efficient method for CO₂ reduction over elemental boron catalysts in the presence of only water and light irradiation through a photothermocatalytic process. Owing to its high solar‐light absorption and effective photothermal conversion, the illuminated boron catalyst experiences remarkable self‐heating. This process favors CO₂ activation and also induces localized boron hydrolysis to in situ produce H₂ as an active proton source and electron donor for CO₂ reduction as well as boron oxides as promoters of CO₂ adsorption. These synergistic effects, in combination with the unique catalytic properties of boron, are proposed to account for the efficiency of the CO₂ reduction. This study highlights the promise of photothermocatalytic strategies for CO₂ conversion and also opens new avenues towards the development of related solar‐energy utilization schemes.