Atomically Dispersed Ce Sites Augmenting Activity and Durability of Fe-Based Oxygen Reduction Catalyst in PEMFC.

In the cathode of proton exchange membrane fuel cells (PEMFCs), Fe and N co-doped carbon (Fe-N-C) materials with atomically dispersed active sites are one of the satisfactory candidates to replace Pt-based catalysts. However, Fe-N-C catalysts are vulnerable to attack from reactive oxygen species, resulting in inferior durability, and current strategies failing to balance the activity and stability. Here, this study reports Fe and Ce single atoms coupled catalysts anchored on ZIF-8-derived nitrogen-doped carbon (Fe/Ce-N-C) as an efficient ORR electrocatalyst for PEMFCs. In PEMFC tests, the maximum power density of Fe/Ce-N-C catalyst reached up to 0.82 W cm-2, which is 41% larger than that of Fe-N-C. More importantly, the activity of Fe/Ce-N-C catalyst only decreased by 21% after 30 000 cycles under H2/air condition. Density functional theory reveals that the strong coupling between the Fe and Ce sites result in the redistribution of electrons in the active sites, which optimizes the adsorption of OH* intermediates on the catalyst and increases the intrinsic activity. Additionally, the admirable radical scavenging ability of the Ce sites ensured that the catalysts gained long-term stability. Therefore, the addition of Ce single atoms provides a new strategy for improving the activity and durability of oxygen reduction catalysts.

A Brief Review of Recent Theoretical Advances in Fe-Based Catalysts for CO2 Hydrogenation.

Catalytic hydrogenation presents a promising approach for converting CO2 into valuable chemicals and fuels, crucial for climate change mitigation. Iron-based catalysts have emerged as key contributors, particularly in driving the reverse water-gas shift and Fischer-Tropsch synthesis reactions. Recent research has focused on enhancing the efficiency and selectivity of these catalysts by incorporating alkali metal promoters or transition metal dopants, enabling precise adjustments to their composition and properties. This review synthesizes recent theoretical advancements in CO2 hydrogenation with iron-based catalysts, employing density functional theory and microkinetic modeling. By elucidating the underlying mechanisms involving metallic iron, iron oxides, and iron carbides, we address current challenges and provide insights for future sustainable CO2 hydrogenation developments.

Recent Progress on Fe-Based Single/Dual-Atom Catalysts for Zn-Air Batteries.

As one of the most competitive candidates for large-scale energy storage, zinc-air batteries (ZABs) have attracted great attention due to their high theoretical specific energy density, low toxicity, high abundance, and high safety. It is highly desirable but still remains a huge challenge, however, to achieve cheap and efficient electrocatalysts to promote their commercialization. Recently, Fe-based single-atom and dual-atom catalysts (SACs and DACs, respectively) have emerged as powerful candidates for ZABs derived from their maximum utilization of atoms, excellent catalytic performance, and low price. In this review, some fundamental concepts in the field of ZABs are presented and the recent progress on the reported Fe-based SACs and DACs is summarized, mainly focusing on the relationship between structure and performance at the atomic level, with the aim of providing helpful guidelines for future rational designs of efficient electrocatalysts with atomically dispersed active sites. Finally, the great advantages and future challenges in this field of ZABs are also discussed.

SO2-Induced Alkali Resistance of FeVO4/TiO2 Catalysts for NOx Reduction.

Selective catalytic reduction of nitrogen oxides with ammonia (NH3-SCR) is an efficient NOx abatement strategy, but deNOx catalysts suffer from serious deactivation due to the coexistence of multiple poisoning substances such as K, SO2, etc. in the flue gas. It is essential to understand the interaction among various poisons and their effects on NOx abatement. Here, we unexpectedly identified the K migration behavior induced by SO2 over K-poisoned FeVO4/TiO2 catalysts, which led to alkali-poisoning buffering and activity recovery. It has been demonstrated that the K would occupy both redox and acidic sites, which severely reduced the reactivity of FeVO4/TiO2 catalysts. After the sulfuration of the K-poisoned catalyst, SO2 preferred to be combined with the surface K2O, lengthened the K-OFe and K-OV, and thus released the active sites poisoned by K2O, thereby preserving an increase in the activity. As a result, for the K-poisoned catalyst, the conversion of NOx increased from 21 to 97% at 270 °C after the sulfuration process. This work contributes to the understanding of the specific interaction between alkali metals and SO2 on deNOx catalysts and provides a novel strategy for the adaptive use of one poisoning substance to counter another for practical NOx reduction.

Characterization of the FeV =O Complex in the Pathway of Water Oxidation.

Hypervalent FeV =O species are implicated in a multitude of oxidative reactions of organic substrates, as well as in catalytic water oxidation, a reaction crucial for artificial photosynthesis. Spectroscopically characterized FeV species are exceedingly rare and, so far, were produced by the oxidation of Fe complexes with peroxy acids or H2 O2 : reactions that entail breaking of the O-O bond to form a FeV =O fragment. The key FeV =O species proposed to initiate the O-O bond formation in water oxidation reactions remained undetected, presumably due to their high reactivity. Here, we achieved freeze quench trapping of six coordinated [FeV =O,(OH)(Pytacn)]2+ (Pytacn=1-(2'-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane) (2) generated during catalytic water oxidation. X-ray absorption spectroscopy (XAS) confirmed the FeV oxidation state and the presence of a FeV =O bond at ≈1.60 Å. Combined EPR and DFT methods indicate that 2 contains a S=3/2 FeV center. 2 is the first spectroscopically characterized high spin oxo-FeV complex and constitutes a paradigmatic example of the FeV =O(OH) species proposed to be responsible for catalytic water oxidation reactions.

Ammonia Synthesis over Fe-Supported Catalysts Mediated by Face-Sharing Nitrogen Sites in BaTiO3-x Ny Oxynitride.

Nitride and hydride materials have been proposed as active supports for the loading of transition metal catalysts in thermal catalytic ammonia synthesis. However, the contribution of nitrogen or hydride anions in the support to the catalytic activity for supported transition-metal catalysts is not well understood, especially for Fe-based catalysts. Here, we report that hexagonal-BaTiO3-x Ny with nitrogen vacancies at face-sharing sites acts as a more efficient support for Fe catalysts for ammonia synthesis than BaTiO3 or BaTiO3-x Hx at 260 °C to 400 °C. Isotopic experiments, in situ measurements, and a small inverse isotopic effect in ammonia synthesis have revealed that nitrogen molecules are activated at nitrogen vacancies formed at the interface between Fe nanoparticles and the support. Nitrogen vacancies on BaTiO3-x Ny can promote the activity of Fe and Ni catalysts, while electron donation and suppression of hydrogen poisoning by BaTiO3-x Hx are significant in the Ru and Co systems.

Dopamine removal from water by advanced oxidative processes with Fe/N-doped carbon nanotubes.

Dopamine (DA) is an important neurotransmitter in the human body, and a subnormal level is associated with some neurological problems, such as Alzheimer's and Parkinson's diseases. Its use as medicine has progressively increased, as well as its appearance in water bodies, such as domestic or hospital effluents. Dopamine has been found to produce neurological and cardiac damage to the animals that have consumed water with its content, so the removal of dopamine from water is of utmost importance to ensure water safety. Advanced oxidative processes (AOPs) are one of the most effective technologies to eliminate hazardous and toxic compounds in wastewater. In this work, Fe-based multi-walled carbon nanotubes (MWCNTs) were synthesized by aerosol-assisted catalytic chemical vapor deposition to be applied in the AOP of DA. MWCNTs (carbon nanotubes) exhibited high catalytic activity in removing DA with 99% of elimination.By increasing 4 times the initial concentration of DA, the removal percentage of the molecule was lower than the original one, which was attributed to the DA saturation of active sites. Even so, the percentage of degradation was high (76.2%).

MIL-100(Fe)-derived catalysts for CO2 conversion via low- and high-temperature reverse water-gas shift reaction.

Fe-derived catalysts were synthesized by the pyrolysis of MIL-100 (Fe) metal-organic framework (MOF) and evaluated in the reverse water-gas shift (RWGS) reaction. The addition of Rh as a dopant by in-situ incorporation during the synthesis and wet impregnation was also considered. Our characterization data showed that the main active phase was a mixture of α-Fe, Fe3C, and Fe3O4 in all the catalysts evaluated. Additionally, small Rh loading leads to a decrease in the particle size in the active phase. Despite all three catalysts showing commendable CO selectivity levels, the C@Fe* catalyst showed the most promising performance at a temperature below 500 °C, attributed to the in-situ incorporation of Rh during the synthesis. Overall, this work showcases a strategy for designing novel Fe MOF-derived catalysts for RWGS reaction, opening new research opportunities for CO2 utilization schemes.

Preparation, characterization, and applications of Fe-based catalysts in advanced oxidation processes for organics removal: A review.

Fe-based catalysts as low-cost, high-efficiency, and non-toxic materials display superior catalytic performances in activating hydrogen peroxide, persulfate (PS), peracetic acid (PAA), percarbonate (PC), and ozone to degrade organic contaminants in aqueous solutions. They mainly include ferrous salts, zero-valent iron, iron-metal composites, iron sulfides, iron oxyhydroxides, iron oxides, and supported iron-based catalysts, which have been widely applied in advanced oxidation processes (AOPs). However, there is lack of a comprehensive review systematically reporting their synthesis, characterization, and applications. It is imperative to evaluate the catalytic performances of various Fe-based catalysts in diverse AOPs systems and reveal the activation mechanisms of different oxidants by Fe-based catalysts. This work detailedly summarizes the synthesis methods and characterization technologies of Fe-based catalysts. This paper critically evaluates the catalytic performances of Fe-based catalysts in diverse AOPs systems. The effects of solution pH, reaction temperature, coexisting ions, oxidant concentration, catalyst dosage, and external energy on the degradation of organic contaminants in the Fe-based catalyst/oxidant systems and the stability of Fe-based catalysts are also discussed. The activation mechanisms of various oxidants and the degradation pathways of organic contaminants in the Fe-based catalyst/oxidant systems are revealed by a series of novel detection methods and characterization technologies. Future research prospects on the potential preparation means of Fe-based catalysts, practical applications, assistive technologies, and impact in AOPs are proposed.

Calcium poisoning mechanism on the selective catalytic reduction of NOx by ammonia over the γ-Fe2O3 (001) surface.

γ-Fe2O3 has an excellent low-temperature selective catalytic reduction (SCR) deNOx performance, but its resistance to alkaline earth metal calcium (Ca) is poor. In particular, the detailed mechanism of Ca poisoning on the γ-Fe2O3 catalyst at the atomic level is not clear. Hence, the density functional theory method was used in this research to investigate the influence mechanism of Ca poisoning on the NH3-SCR over the γ-Fe2O3 catalyst surface. The findings reveal that NH3, NO, and O2 molecules can bind to the γ-Fe2O3 (001) surface to generate coordinated ammonia, monodentate nitroso, and adsorption oxygen species, respectively. The main active site is Fe1-top. For the γ-Fe2O3 with Ca poisoning, the Ca atom has a high adsorption energy on the surface of γ-Fe2O3 (001), which covers the catalyst surface and reduces the active sites. The presence of Ca atom decreases the adsorption performance of NH3, while slightly improving the NO and O2 adsorption. In particular, the Ca atom restrains the NH3 activation and NH2 formation, which is detrimental to the NH3-SCR process.

Preparation of Nitrogen Doped Biochar-Based Iron Catalyst for Enhancing Gasoline-Range Hydrocarbons Production.

Developing catalysts to obtain high space time yield (STY) of gasoline-range hydrocarbons via Fischer-Tropsch synthesis (FTS) is a huge challenge due to the restriction of Anderson-Schulz-Flory distribution. Herein, a nitrogen doped biochar-based iron catalyst was synthesized by a one-step method using sugar cane bagasse as carbon precursor, which exhibited an excellent gasoline STY of 8.65 gC5-12 gFe-1 h-1, exceeding most reported catalysts. A strong positive relationship between the amount of pyrrolic N and long-chain hydrocarbons selectivity was displayed. The characterization results indicated that pyrrolic N configuration on anchor sites tuned effectively the dispersion of iron species and metal-support interaction as well as CO adsorption, improving the FTS performance.

Role of C-Defective Sites in CO Adsorption over ϵ-Fe2 C and η-Fe2 C Fischer-Tropsch Catalysts.

Herein, we report the crucial importance of C-defective sites on the CO adsorption over ϵ-Fe2 C and η-Fe2 C Fischer-Tropsch catalysts via systematic DFT calculations. The simulated XRD and Wulff construction show the significant differences in their equilibrium shapes and most exposed surfaces. It is observed that the ϵ-Fe2 C exposes a high proportion (89 %) of facets (1 2 ‾ 1) with similar structure to that of η-Fe2 C (011) which has been proved to be the active surface of CO activation.

NO oxidation over Fe-based catalysts supported on montmorillonite K10, γ-alumina and ZSM-5 with gas-phase H2O2.

The catalytic gas-phase H2O2 oxidation of NO was achieved over Fe-based catalysts supported on montmorillonite K10, γ-alumina and ZSM-5. ESR tests illustrate that the three catalysts can catalyze decomposition of H2O2 yielding highly reactive hydroxyl radicals, of which Fe/K10 has the fastest rate, followed by Fe/γ-alumina. Fe3+ in Fe/K10 and Fe/γ-alumina show lower density of electron cloud due to a strong interaction between Fe3+ and the support, which benefits the electron transfer from the H2O2 to Fe3+, thus favoring the production of hydroxyl radicals. Fe species exist on the surface of Fe/K10 mainly in the form of Fe2O3, whereas Fe species of Fe/γ-alumina and Fe/ZSM-5 exist mainly in the form of Fe3O4, and it is found that Fe2O3 is more active than Fe3O4 in catalytic gas-phase H2O2 oxidation of NO. Interestingly, Fe/ZSM-5 has the lowest efficiency in generating hydroxyl radicals, its NO removal efficiency is 90%, which is much higher than 47.5% for Fe/γ-alumina and 62.3% for Fe/K10. In-situ IR results suggested that Fe/ZSM-5 are dual functional in oxidation of NO, that is, whether both Fe ion sites and Brønsted acid sites collectively provide the catalytic functionality. In the meantime, a possible reaction mechanism on catalytic gas-phase H2O2 oxidation of NO over Brønsted acid sites is proposed.

Reductive Transformation of Layered-Double-Hydroxide Nanosheets to Fe-Based Heterostructures for Efficient Visible-Light Photocatalytic Hydrogenation of CO.

Conversion of syngas (CO, H2 ) to hydrocarbons, commonly known as the Fischer-Tropsch (FT) synthesis, represents a fundamental pillar in today's chemical industry and is typically carried out under technically demanding conditions (1-3 MPa, 300-400 °C). Photocatalysis using sunlight offers an alternative and potentially more sustainable approach for the transformation of small molecules (H2 O, CO, CO2 , N2 , etc.) to high-valuable products, including hydrocarbons. Herein, a novel series of Fe-based heterostructured photocatalysts (Fe-x) is successfully fabricated via H2 reduction of ZnFeAl-layered double hydroxide (LDH) nanosheets at temperatures (x) in the range 300-650 °C. At a reduction temperature of 500 °C, the heterostructured photocatalyst formed (Fe-500) consists of Fe0 and FeOx nanoparticles supported by ZnO and amorphous Al2 O3 . Fe-500 demonstrates remarkable CO hydrogenation performance with very high initial selectivities toward hydrocarbons (89%) and especially light olefins (42%), and a very low selectivity towards CO2 (11%). The intimate and abundant interfacial contacts between metallic Fe0 and FeOx in the Fe-500 photocatalyst underpins its outstanding photocatalytic performance. The photocatalytic production of high-value light olefins with suppressed CO2 selectivity from CO hydrogenation is demonstrated here.