Fe Incorporation Research Articles

Iron nanoparticle engineered N-doped graphitic carbon composite as a binary electrocatalyst for overall water splitting and supercapacitor

In this study, we report on the tailored synthesis of nitrogen-(N)-doped carbon and iron-(Fe)-loaded N-doped carbon composites and their use for the oxygen evolution reaction (OER), hydrogen evolution reaction (HER), overall electrochemical water splitting, and supercapacitors. FE-SEM and HR-TEM analyses reveal that the developed composite material exhibits a core-shell structure with enhanced porosity upon Fe incorporation. By adjusting the ratio of Fe to N-doped carbon in the composites, it was identified that the catalyst 5Fe@NC demonstrates outstanding electrochemical activity alongside commendable stability. Specifically, the 5Fe@NC electrocatalyst achieves current densities of +10 mAcm−2 and -10 mAcm−2 in alkaline electrolyte with minimal overpotentials of 376 mV and 520 mV, respectively. Notably, impressive Tafel slopes of 84 mV/dec and 212 mV/dec for the OER and HER were obtained, indicating superior kinetic activity of the developed composite materials. As a supercapacitor, 5Fe@NC electrode material exhibits a measurable specific capacitance of 294 F/g at 0.5 A/g current density with excellent durability (78 % retention after 1000 charge-discharge cycles). Furthermore, we conducted assessments on stability, charge transfer resistance, and ECSA, yielding excellent outcomes. This work successfully demonstrates a highly effective dual-purpose electrocatalyst prepared from indole and furfural (heterocycles abundant in biomass), exhibiting excellent electrochemical activity and stability in facilitating HER and OER within alkaline electrolytes.

Assessment of acid catalytic properties of ferrosilicate MFI zeolite by methanol-to-hydrocarbon conversion.

Four representative synthetic methods were employed to prepare Fe-containing siliceous MFI zeolites. The obtained Fe-MFI zeolites exhibited markedly different catalytic performances in the methanol-to-hydrocarbon (MTH) conversion reaction depending on the type of Fe incorporation within the siliceous framework. The catalytically active Brønsted acid sites were analyzed using pyridine adsorption experiments combined with Fourier transform infrared spectroscopy, providing characteristic signal intensities according to the acid-base interactions. Based on the MTH conversion results and acidity analyses, a suitable synthetic method was identified for the incorporation of Fe within the MFI zeolite framework. However, compared to other catalytic reactions, structural analyses by transmission electron microscopy, ultraviolet-visible spectroscopy, and X-ray absorption spectroscopy were much less conclusive.

Identifying the dynamic behaviors in complete reconstruction of Co-based complex precatalysts during electrocatalytic oxygen evolution

Transition metal-based nanomaterials have emerged as promising electrocatalysts for oxygen evolution reaction (OER). Considerable research efforts have shown that self-reconstruction occurs on these nanomaterials under operating conditions of OER process. However, most of them undergo incomplete reconstruction with limited thickness of reconstruction layer, leading to low component utilization and arduous exploration of real catalytic mechanism. Herein, we identify the dynamic behaviors in complete reconstruction of Co-based complexes during OER. The hollow phytic acid (PA) cross-linked CoFe-based complex nanoboxes with porous nanowalls are designed because of their good electrolyte penetration and mass transport ability, in favor of the fast and complete reconstruction. A series of experiment characterizations demonstrate that the reconstruction process includes the fast substitution of PA by OH− to form Co(Fe)(OH)x and subsequent potential-driven oxidation to Co(Fe)OOH. The obtained CoFeOOH delivers a low overpotential of 290 mV at a current density of 10 mA cm−2 and a long-term stability. The experiment results together with theory calculations reveal that the Fe incorporation can result in the electron rearrangement of reconstructed CoFeOOH and optimization of their electronic structure, accounting for the enhanced OER activity. The work provides new insights into complete reconstruction of metal-based complexes during OER and offers guidelines for rational design of high-performance electrocatalysts.

Physical insight into the enhanced urea electrooxidation using Ni and Fe-based LDH, LDO, and hydroxides under different dissolved gas saturation conditions in electrolyte

The production of green hydrogen is one of the most demanding and challenging for modern technology. A promising and an effective approach is electrocatalytic anodic urea oxidation reaction to generate hydrogen at cathode under alkaline electrolysis condition. However, it remains crucial for the development of active and stable electrocatalysts for efficient urea oxidation. In this study, we employed the hydrothermal synthesis route for NiFe LDH, NiFe LDO, and Ni(OH)2. The superior performance of NiFe LDH compared to other catalysts is observed due to easy charge transfer facilitated by Fe ions. Moreover, Fe incorporation prevents surface poisoning of the electrocatalyst, resulting in increased activity and stability for electrocatalytic urea oxidation reaction. The influence of different electrolyte environments on the performance of urea-based electrolyzers for sustainable hydrogen production and management of urea-rich wastewater has been measured for the first time by varying oxygen saturation and nitrogen purging conditions. In cyclic voltammetry studies, O2-saturated and purging conditions outperformed N2 gas saturation or purging. The findings of this study provide valuable insight into the design of practical and environmentally friendly urea electrooxidation systems.

Electrolyte-Induced Fe-Doping of LaNiO3 Model Surfaces for Water Electrolysis

Renewable energy needs to be store in different energy forms for the energy transition away from fossil fuels. One of most promising forms is chemicals such as H2 and C-based fuels obtained via electrochemical reactions. The common hinderance in such reactions is the sluggish oxygen evolution reaction (OER), which causes low energy efficiency in conversion devices. Developing highly active, earth-abundant OER electrocatalysts in alkaline media is necessary to boost the performance of such devices. Fe ion content in electrolyte is known to influence the OER-activity of metal oxide electrocatalysts. For example, the Fe incorporation in NiOOH is a well-established and important effect for OER.[1] Here, we present the effect of absorbed Fe on the OER activity of the epitaxial Ni-surface terminated LaNiO3 thin films. The correlation between surface species and OER activity of electrocatalysts was investigated using surface-sensitive low-energy ion scattering and X-ray photoemission spectroscopies. We observe more than an order-of-magnitude boost in OER activity during initial cycling, from 0.15 mAcm-2 to 3.40 mAcm-2 at 1.60 V vs. reversible hydrogen electrode. The activity increase was mainly caused by the incorporation of up to 5 % Fe at the top surface of LaNiO3 film (less than ~1 nm) even though only a very trace amount of Fe ion, 30 ppb, is present in the 0.1 M electrolyte of high purity KOH 99.99 %. Our results demonstrate that the disordered active surface phase, which develops even on single crystalline surfaces, is a complex interplay between the as-prepared (surface) crystalline structure, composition of the solid electrocatalyst and the liquid electrolyte, and has strong impact on the final OER activity, implying that we need to think differently about the crystalline electrocatalysts: crystalline bulk and dynamically changing surface layer.[1] L. Trotochaud, S.L. Young, J.K. Ranney, S.W. Boettcher, Nickel–Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation, J. Am. Chem. Soc. 136 (2014) 6744–6753.

Dynamic Activity and Stability of Transition Metal (oxy)Hydroxide Oxygen Evolution Electrocatalysts Under Steady and Intermittent Operation

The oxygen evolution reaction (OER) plays a critical role in several energy conversion technologies, requiring catalysts that combine high activity with stability for successful commercialization. Catalysts from first-row transition metal oxides have garnered considerable attention in this context. Their noteworthy OER activity and stability in alkaline environments position them as a more economical option than their counterparts in acidic media. However, recent studies have shown that these materials tend to experience significant dissolution issues and undergo changes in their chemical composition, a phenomenon observed even during steady-state operation.1–3 Addressing these challenges is essential for advancing commercial energy conversion technologies, which often face intermittent loads and reverse currents. A deeper understanding of the dynamic reconstruction under fluctuating conditions is crucial for developing more durable and efficient electrocatalytic materials.4 In this work, we investigate the dynamic performance of nickel cobalt (oxy)hydroxide electrocatalytic films containing iron active sites in alkaline media under steady and intermittent operation. First, we systematically examine the changes in OER catalytic activity in a typical three-electrode configuration, focusing on the incorporation and redissolution of iron and cerium during different electrochemical conditioning methods. As shown in Figure 1a, conditioning using chronopotentiometry decreases the OER overpotential without significantly shifting the redox peak. In contrast, conditioning using cyclic voltammetry significantly shifts the redox peak position (Figure 1b). These differences are attributed to the (oxy)hydroxide film thickness, which forms in situ during conditioning and affects the Fe dissolution and incorporation rates based on the conditioning method.5 We use different analytical techniques to probe chemical transformations during conditioning. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS) are utilized to analyze compositional changes in the electrocatalytic films. Moreover, inductively coupled plasma mass spectrometry (ICP-MS) tracks metal dissolution.Next, we utilize an electrochemical flow electrolyzer with a zero-gap configuration, integrated with online ICP-MS and post-experimental TOF-SIMS and XPS, to study the reconstruction of these electrocatalysts under intermittent conditions. A NiFe anode operating in 6 M KOH with 1 ppm of Fe3+ shows a 40-mV change after 120 cycles of alternating low and high currents, including a simulated shutdown step (Figure 1c). This cell potential change, becoming more negative with continued cycling (Figure 1d), is attributed to the shutdown step. Our findings underscore how operating conditions affect the dynamic reconstruction of electrocatalytic materials, offering critical insights for developing more robust and resilient materials suitable for commercial applications.

The impact of surface-impregnated versus support-dispersed Fe in Fe–Ni/γ-Al2O3 catalysts for partial oxidation of methane: Insights into the effect of Fe incorporation method on coking and on the reaction mechanism

Two sets of Fe-modified Ni/γ-Al2O3 catalysts were prepared and tested in partial oxidation of methane. In one set, Fe was co-impregnated on the surface (NiFe) and in the other set Fe was incorporated in the support bulk (Ni/Fe). The two types showed significantly different coking resistance and performance. While Fe well dispersed in the support bulk significantly enhanced coking resistance, Fe co-impregnated with Ni on the surface enhanced the rate of coke deposition on the catalysts’ surfaces. The impact of Fe in the Ni/Fe catalysts is referred to its partially reduced ions (Fe2+) in redox reactions, and to the Ni-support strong interaction retarding the coke formation pathways. On the contrary, carbon formation on the NiFe catalysts is referred to the formation of Ni–Fe alloy particles which may block Ni active sites and can promote cracking of methane as well as CO molecules resulting in higher rates of coking.

Photocatalytic Enhancement for CO2 Reduction Using Au Nanoparticles Supported on Fe‐Doped SrTiO3−δ Perovskite

This study focuses on the use of Au nanoparticles supported on the SrTiO3−δ perovskite doped with Fe ions as a photocatalyst for CO2 reduction and methanol production using water as the hydrogen supplier. The photocatalytic evaluation of the synthesized materials shows that Au nanoparticles supported on the SrTi(1−x)FexO3−δ perovskites can enhance photocatalytic CO2 reduction. The sample with the doping level x = 0.125 has the highest methanol production, 9.5 times more than the undoped sample and 3.5 times more than its counterpart without Au nanoparticles. The results of the DFT + U calculations show that the contributions from the iron atoms states reduce the energy gap in the perovskite composite, SrTi(1−x)FexO3−δ. Additionally, Fe incorporation endows the system with the capacity to create electron–hole pairs via direct band transitions at the high‐symmetry point R with the doping levels of x = 0.125 and x = 0.250.

Tunning MIL-101(Cr) MOF polymorphism towards efficient adsorption and localized Fenton-like degradation of para-nitroaniline by Fe incorporation

The employment of metal–organic frameworks (MOFs) in the context of eliminating organic contaminants from water has garnered significant interest in contemporary research. This study investigated the impact of varying quantities of iron on the MIL-101(Cr) adsorbent. For the first time, a polymorphic Cr/Fe-MOF was utilized for the adsorption and localized Fenton-like degradation of p-nitroaniline (PNA). Importantly, the Fe centers exhibited a ternary role of (i) transforming MIL-101 into MIL-53lt morphology, (ii) boosting PNA adsorption on the MIL(Cr) material, and (iii) enabling the Fenton-like decomposition of the adsorbed PNA in reduced solution volume. Cr:Fe(50:50) exhibited the highest adsorption capacity of 378.9 mg/g, notwithstanding its smaller surface area (SBET = 8.9 m2/g). Overall, adsorption kinetics and isotherms correlated better with pseudo-second-order and Langmuir models, respectively. The adsorption mechanism was attributed to breathing effect, H-bonding and π-π interaction. Besides, PNA degradation kinetics stood at 0.21 min−1, and the reactive oxygen species were identified as •OH, •O2– and 1O2. During continuous removal of PNA, the Cr:Fe(50:50) MOF immobilized onto cotton met the environmental discharge standard (1 mg/L) up to 52 bed volumes (initial P = 10.0 mg/L at 1 mL/min). This study not only presents a superior polymorphic MOF adsorbent but also promotes the fabrication of localized Fenton-like catalysts for the removal of organic contaminants in wastewater.

Introducing a novel catalyst for efficient conversion of CO2 into syngas through reverse-water-gas-shift (RWGS) reactions based on highly mesoporous structures MCM-41: Influence of the Fe incorporation

The RWGS is the first step in CO2 hydrogenation. This process converts CO2 into valuable compounds, such as methanol, to address the global issue of CO2 emissions. In this research, the performance of a Cu-Fe bimetallic catalyst mounted onto MCM-41 support in RWGS was investigated. Our results demonstrate that MCM-41′s high specific surface area is advantageous for dispersing active metals and preventing their sintering. The Cu-Fe supported on MCM-41 samples are characterized by Scanning Electron Microscopy (SEM), ex situ X-ray Diffraction (XRD), Brunner–Emmet–Teller (BET), and Temperature Programmed Reduction (TPR). In order to investigate the catalytic activity, key variables including a temperature range of 400–600 °C, different H2/CO2 ratios, and various gas hourly space velocities (GHSV) at atmospheric pressure were assessed. In this study, excellent CO2 conversion was attained at a high GHSV (96,000 ml g-1h−1), which is advantageous for the design of smaller reactor volumes. In comparison to industrial Copper-Zinc catalysts and iron-free copper-supported MCM-41 catalysts, which suffer from a high sintering rate at temperatures above 300 °C, adding Iron (Fe) to the copper could increase the catalyst's activity and stability in terms of CO2 conversion and CO selectivity due to the formation of a Cu-Fe alloy. The novelty of this study lies in the assessment of the benefits afforded by bimetallic Cu-Fe catalysts in conjunction with high surface area MCM-41. Also, three different ratios of Cu-Fe (10-1, 7-1, 4-1) were considered for our experiments. The Cu-Fe = 10-1 ratio reached the highest CO2 conversion and CO selectivity value in 600 °C with amounts of 49 % and 99.7 %, respectively.

A Co and Fe bimetallic MOF with enhanced electrocatalytic oxygen evolution performance: exploring the electronic environment modifications upon Fe incorporation

The incorporation of iron into the cobalt-based metal–organic framework modifies the electronic environment and the resulting bimetallic MOF exhibits enhanced oxygen evolution reaction performance.

Band gap tunability and optical properties of sol-gel derived Fe-doped CeO2 films

In this study, CeO2 films incorporating different amounts of Fe (3 %, 5 %, 10 %) were deposited on glass substrates by using the sol-gel method. The physical properties of the films were scrutinized by employing characterization techniques such as X-ray diffractometer (XRD), scanning electron microscopy (SEM) and ultraviolet–visible spectroscopy (UV–vis), respectively. The change of structural parameters was examined using Scherrer, W–H and SSP methods. A decrease in crystallite size was observed with Fe incorporation in all three methods. SEM images presented the homogeneity on the surface increased with increasing Fe doping. Optical measurements showed that the band gap decreased from 3.17 eV to 2.55 eV and at the same time all optical constants decreased with increasing Fe content. These results suggest that the optical properties of CeO2 films can be tuned by Fe doping. It means that Fe-doped CeO2 films will play an important role in optoelectronic device applications.

Regulating acid properties of ZSM-5 nanosheets by Fe incorporation towards high-performance alkylation of benzene with methanol

A clear understanding of the acidity-activity relationship is an important prerequisite for designing functional materials in alkylation of benzene with methanol. Herein, a series of b-axis-oriented [Fe/Al]-MFI nanosheets with similar thickness but varied acidities were prepared by tuning Fe incorporation to systematically study the effect of acidity on their alkylation performance. Comprehensive physiochemical studies demonstrate that tetrahedral framework type Fe species are dominated. The incorporation of Fe significantly weakens the strong acid strength of zeolite thus endowing the samples with proper acidity, consequently showing a strong inhibition effect on the by-product ethylbenzene. Moreover, a long-term stable operation (>300 h) is further achieved over the [Fe]-S-1 nanosheets by optimizing the content of framework Fe. This work elucidates the important relationship between acidity and alkylation activity.

Tuning Ni-Pyrazolate Frameworks by Post-Synthetic Fe-Incorporation for Oxidase-Mimicking H2 O2 Activation.

The introduction of iron ionic sites by metal exchange of defective homometallic nickel pyrazolate frameworks generates non-precious, Earth-abundant, first-row heterometallic Fe/Ni-pyrazolate frameworks. The Fe incorporation at the Ni nodes of the framework allows to control the hydrogen peroxide activation, minimizing its decomposition and O2 liberation, occurring at the homometallic Ni nodes. The generation of Fe-OH reactive oxygen species at the heterometallic Fe/Ni nodes is demonstrated by the higher activity in the proof-of-concept oxidation of 1-phenylethanol to acetophenone in an aqueous medium.

Effects of metal-ion substitution on the structural, morphological, and electrochemical properties of LiFexZnyMn2−x-yO4 (x, y = 0.25 or 0.75)

The oxides LiMn2O4, LiFe0.75Zn0.25MnO4, and LiFe0.25Zn0.25Mn1.5O4, referred to as LMO, LFZMO 0.75–0.25, and LFZMO 0.25–0.25, were synthesized at 800 °C using ultrasound-assisted thermal decomposition of nitrates (UA-TDN). X-ray diffraction (XRD) analyses confirmed the spinel structure (Fd3m space group) for all materials. Raman spectroscopy validated the characteristic absorption bands of the spinel phase. Energy-dispersive spectroscopy (EDS) verified the uniform distribution of Fe, Zn, Mn, and O in all samples and proved the expected stoichiometry for the different oxides. Scanning electron microscopy (SEM) images showed irregular polyhedral agglomerates in the synthesized oxides, with grain sizes ranging from approximately 600 to 800 nm. Electrochemical characterization was performed under N2 and O2 atmospheres, revealing electron-withdrawing effects with increasing iron content in the oxide composition. LFZMO 0.75–0.25, with a higher iron content, displayed better performance than LMO and LFZMO 0.25–0.25 in terms of discharge capacity and cycling performance at various rates. The greater discharge capacity of LFZMO 0.75–0.25 (47 mA h g −1) was in line with the cyclic voltammetry findings, wherein lower energy (∆GLi+/ Li0= 55.5 kJ mol−1) for lithium insertion correlated with an increased discharge capacity. Electrochemical Impedance Spectroscopy (EIS) was employed to determine diffusion constants, providing insights into Li+ insertion kinetics in the cathodic electrode and highlighting the significant influence of Zn and Fe incorporation on the lithium manganese oxide. Our findings are intriguing as the diffusion coefficient of DLi+ in LFZMO 0.75–0.25 (2.3 ×10−12 cm2 S−1) surpasses that of LMO (8.5 ×10−14 cm2 S−1) and LFZMO 0.25–0.25 (9.4 ×10−18 cm2 S−1). This observation further elucidates the more positive formal potential for Li+ insertion in LFZMO 0.75–0.25.

Elucidating the Mechanism of Fe Incorporation in In Situ Synthesized Co-Fe Oxygen-Evolving Nanocatalysts.

Ni- and Co-based catalysts with added Fe demonstrate promising activity in the oxygen evolution reaction (OER) during alkaline water electrolysis, with the presence of Fe in a certain quantity being crucial for their enhanced performance. The mode of incorporation, local placement, and structure of Fe ions in the host catalyst, as well as their direct/indirect contribution to enhancing the OER activity, remain under active investigation. Herein, the mechanism of Fe incorporation into a Co-based host was investigated using an in situ synthesized Co-Fe catalyst in an alkaline electrolyte containing Co2+ and Fe3+. Fe was found to be uniformly incorporated, which occurs solely after the anodic deposition of the Co host structure and results in exceptional OER activity with an overpotential of 319 mV at 10 mA cm-2 and a Tafel slope of 28.3 mV dec-1. Studies on the lattice structure, chemical oxidation states, and mass changes indicated that Fe is incorporated into the Co host structure by replacing the Co3+ sites with Fe3+ from the electrolyte. Operando Raman measurements revealed that the presence of doped Fe in the Co host structure reduces the transition potential of the in situ Co-Fe catalyst to the OER-active phase CoO2. The findings of our facile synthesis of highly active and stable Co-Fe particle catalysts provide a comprehensive understanding of the role of Fe in Co-based electrocatalysts, covering aspects that include the incorporation mode, local structure, placement, and mechanistic role in enhancing the OER activity.

Role of Native Defects in Fe-Doped β-Ga2O3.

Iron impurities are believed to act as deep acceptors that can compensate for the n-type conductivity in as-grown Ga2O3, but several scientific issues, such as the site occupation of the Fe heteroatom and the complexes of Fe-doped β-Ga2O3 with native defects, are still lacking. In this paper, based on first-principle density functional theory calculations with the generalized gradient approximation approach, the controversy regarding the preferential Fe incorporation on the Ga site in the β-Ga2O3 crystal has been addressed, and our result demonstrates that Fe dopant is energetically favored on the octahedrally coordinated Ga site. The structural stabilities are confirmed by the formation energy calculations, the phonon dispersion relationships, and the strain-dependent analyses. The thermodynamic transition level Fe3+/Fe2+ is located at 0.52 eV below the conduction band minimum, which is consistent with Ingebrigtsen's theoretical conclusion, but slightly smaller than some experimental values between 0.78 eV and 1.2 eV. In order to provide direct guidance for material synthesis and property design in Fe-doped β-Ga2O3, the defect formation energies, charge transitional levels, and optical properties of the defective complexes with different kinds of native defects are investigated. Our results show that VGa and Oi can be easily formed for the Fe-doped β-Ga2O3 crystals under O-rich conditions, where the +3 charge state FeGaGai and -2 charge state FeGaOi are energetically favorable when the Fermi level approaches the valence and conduction band edges, respectively. Optical absorption shows that the complexes of FeGaGai and FeGaVGa can significantly enhance the optical absorption in the visible-infrared region, while the energy-loss function in the β-Ga2O3 material is almost negligible after the extra introduction of various intrinsic defects.

Activating Fe activity and improving Ni activity via C3N4 substrate in alkaline oxygen evolution catalyzed by Ni-Fe phosphide

Ni phosphides have recently attracted considerable attention as promising catalysts for the oxygen evolution reaction (OER) and are generally promoted by Fe incorporation. However, the catalytic performance of nickel phosphide still does not meet the desired expectations. Additionally, the catalytic activity of iron (Fe) is insignificant and can be disregarded. In this study, we used C3N4 as a carbon substrate to modulate the 3d electron configurations and adsorption properties of Ni and Fe. Density functional theory (DFT) analysis reveals that the catalytic performance of Ni sites can be enhanced by utilizing the C3N4 substrate. Surprisingly, the Fe sites can also be activated to catalyze OER through a direct O2 mechanism and the catalytic activity of Fe is found to surpass that of Ni. As a result, the FeNi-C3N4-P catalyst demonstrated remarkable catalytic performance for OER. It exhibited a Tafel slope of 40.4 mV dec−1, an overpotential of 235 mV at 100 mA cm−2, and exhibited exceptional stability. This study highlights the activation of Fe and the enhancement of Ni by utilizing nitrogen-containing carbon substrates. This strategy offers promising prospects for the development of efficient Ni/Fe-based OER catalysts.

Spatially and Chemically Resolved Visualization of Fe Incorporation into NiO Octahedra during the Oxygen Evolution Reaction.

The activity of Ni (hydr)oxides for the electrochemical evolution of oxygen (OER), a key component of the overall water splitting reaction, is known to be greatly enhanced by the incorporation of Fe. However, a complete understanding of the role of cationic Fe species and the nature of the catalyst surface under reaction conditions remains unclear. Here, using a combination of electrochemical cell and conventional transmission electron microscopy, we show how the surface of NiO electrocatalysts, with initially well-defined surface facets, restructures under applied potential and forms an active NiFe layered double (oxy)hydroxide (NiFe-LDH) when Fe3+ ions are present in the electrolyte. Continued OER under these conditions, however, leads to the creation of additional FeOx aggregates. Electrochemically, the NiFe-LDH formation correlates with a lower onset potential toward the OER, whereas the formation of the FeOx aggregates is accompanied by a gradual decrease in the OER activity. Complementary insight into the catalyst near-surface composition, structure, and chemical state is further extracted using X-ray photoelectron spectroscopy, operando Raman spectroscopy, and operando X-ray absorption spectroscopy together with measurements of Fe uptake by the electrocatalysts using time-resolved inductively coupled plasma mass spectrometry. Notably, we identified that the catalytic deactivation under stationary conditions is linked to the degradation of in situ-created NiFe-LDH. These insights exemplify the complexity of the active state formation and show how its structural and morphological evolution under different applied potentials can be directly linked to the catalyst activation and degradation.

High-throughput and cost-effective method for production of high-quality semi-insulating InP substrates

A novel technique for preparation of high-resistivity indium phosphide (InP) via post-growth treatment of undoped n-type wafers is presented. The method includes the deposition of a controlled quantity of iron on both faces of as-cut wafers by a simple chemical bath, and the subsequent Fe diffusion by thermal annealing. The reproducible low - to – high resistivity conversion is explained considering two simultaneous phenomena: the annealing-controlled in-diffusion of Fe deep acceptors and the out-diffusion of hydrogen-related shallow donors. Differently from standard Fe-doped melt-grown InP single crystals, this process does not suffer from segregation, thus the Fe-concentration is constant from wafer to wafer, with no striations and radial gradients deriving from the convex solid–liquid interface during growth. Main advantages of the developed process are: i) an entire undoped InP boule may be sliced and converted to semi-insulating, which makes the process cost-effective; ii) reproducible and uniform semi-insulating properties from batch to batch of wafers; iii) the Fe incorporation is precisely controlled, and minimized, so that electrical characteristics of Fe-diffused wafers are superior to those of traditional semi-insulating melt-grown InP crystals doped via addition of elemental Fe to the melt.