Iridium oxide fabrication and application: A review

Despite the scarcity and cost of iridium oxide,it is still the material of choice in numerous fields of science and applications,including capacitors,electrochromism,sensors,and various oxidation electrocatalysis(e.g.,chlorine evolution reaction,detoxification,and oxygen evolution reaction).Such versatility is attributed to the distinct features of iridium oxides,such as their activity,biocompatibility,conductivity,and durability.The features and properties of iridium oxides are strongly dependent on the fabrication method.In this review,methodologies relating to the synthesis and fabrication of solid-state iridium oxides have been thoroughly collected and discussed.Structuring and crystallization techniques for iridium oxides are also noted.At the end of the review,the effects of utilizing a certain fabrication method on the characteristics of the iridium oxide product are recapitulated,together with the recommended application of the product in various fields.

Boron-doped amorphous iridium oxide with ultrahigh mass activity for acidic oxygen evolution reaction

Oxygen evolution reaction(OER), as the primary anodic reaction, plays a critical role in many electrochemical energy conversion processes. As the state-of-the-art OER catalysts, iridium-based materials are largely hindered from practical applications mainly due to the extreme scarcity of iridium. Here we demonstrate the successful fabrication of boron-doped amorphous iridium oxide(IrO_(x)-B) via a facile boric acid-assisted method, which realizes an ultrahigh OER mass activity of 2779 A g^(-1)Irat 300 mV overpotential, representing one of the best acidic OER catalysts reported so far.It is found that boric acid can not only facilitate the exposure of Ir, but also dope the amorphous IrOxwith a form of metaborate, which could further modify the electronic and local ligand structure of Ir for the improved intrinsic activity. Interestingly, the reported strategy is universal that can be applied to improve other metal oxide OER catalysts, highlighting a versatile strategy for creating high-performance electrocatalysts with ultrahigh mass activity for OER and beyond.

Fabrication of iridium oxide neural electrodes at the wafer level

Electro-deposition, electrical activation, thermal oxidation, and reactive ion sputtering are the four primary methods to fabricate iridium oxide film. Among these methods, reactive ion sputtering is a commonly used method in standard micro-fabrication processes. In different sputtering conditions, the component, texture, and electrochemistry character of iridium oxide varies considerably. To fabricate the iridium oxide film compatible with the wafer-level processing of neural electrodes, the quality of iridium oxide film must be able to withstand the mechanical and chemical impact of post-processing, and simultaneously achieve good performance as a neural electrode. In this study, parameters of sputtering were researched and developed to achieve a balance between mechanical stability and good electrochemical characteristics of iridium oxide film on electrode. Iridium oxide fabricating process combined with fabrication flow of silicon electrodes, at wafer-level, is introduced to produce silicon based planar iridium oxide neural electrodes. Compared with bare gold electrodes, iridium oxide electrodes fabricated with this method exhibit particularly good electrochemical stability, low impedance of 386 kW at 1 kH z, high safe charge storage capacity of 3.2 m C/cm^2, and good impedance consistency of less than 25% fluctuation.

Iridium Oxide Film-Enhanced Impedance Immunosensor for Rapid Detection of Carcinoembyronic Antigen

A simple, rapid and sensitive impedance immunosensor based on iridium oxide （IrOx） thin film for the detection of carcinoembyronic antigen （CEA） in human sera has been proposed. Gold electrode was electrochemically modified with IrOx thin film and simultaneously functionalized with protein A （PA） to bind anti-CEA antibodies in an orientated way. It has been found that the antibody loading amount was dependent on the PA concentration and the deposition time of IrOx matrix. Under the optimized experimental conditions, the electron transfer resistances obtained were linearly related to the CEA concentration ranging from 36.2 to 460.0 ng/mL, with a detection limit of 28.0 ng/mL. Analytical results of clinical samples from cancer patients show that the proposed immunoassay is reasonably comparable with the chemiluminescence immunoassay （CLIA）, indicating the feasibility of using the proposed method for CEA immunoassay in clinical laboratory.

Epitaxial interface stabilizing iridium dioxide toward the oxygen evolution reaction under high working potentials

Proton exchange membrane water electrolyzer(PEMWE)driven by renewable electricity is a promising technique toward green hydrogen production,but the corrosive environment and high working potential pose severe challenges for developing advanced electrocatalysts for the oxygen evolution reaction(OER).Although Ir-based materials possess relatively balanced activity and stability for the OER,their dissolution behavior cannot be neglected,in particular under high working potentials.In this work,iridium dioxide(IrO_(2))nanoparticles(NPs)were anchored on the surface of exfoliated h-boron nitride(BN)nanosheets(NSs)toward the OER reaction in acid media.Highly active Ir(V)species were stabilized by the epitaxial interface between IrO_(2)and h-BN,and therefore the IrO_(2)/BN delivered stable performance at increased working potentials,while the activity of bare IrO_(2)NPs without h-BN support decreased rapidly.Also,the smaller lattice spacing of h-BN induced compressive strain for IrO_(2),resulting in improved activity.Our results demonstrate the feasibility of stabilizing highly active Ir(V)species for the OER in acid media by constructing robust interface and provide new possibilities toward designing advanced heterostructured electrocatalysts.

INVESTIGATION OF SURFACE MORPHOLOGY, STRUCTURE AND ELECTROCATALYTIC PROPERTIES FOR O_2 EVOLUTION OF TITANIUM BASED IrO_2+Ta_2O_5 COATINGS

Titanium based IrO2 +Ta2O5 oxide anodes with different compositions and pyrolysis temperatures were prepared by termodecompoisition method. By using X-ray diffraction (XRD), the structure and texture coefficient of the coatings, TC(hkl), of IrO2 rutile crystal have been tested. It showed that, the crystallization processes of IrO2 and Ta2O5 in xIrO2 +(100-x) Ta2 O5 (x is in mol%) films affected and confined each other.In the mixed system, IrO2 rutile phase existed as a solid solution with Ta, and attained the maximum solubility when x=70mol%, i.e. for the coating of 70% IrO2 +Ta2O5.For the coatings of low iridium content or at low preparing tem pemture, (110) and (101) pwtered orientations were dominant. However, preferred growth of IrO2 weakened with increasing either iridium content or temperature. Three typical surface morphologies were observed by using scanning electron tnicroscopy(SEM). The crystallite size of the mixed oxide coatings were finest for the the film of 70%IrO2 +30%Ta2O5,and decreased with the pyrolysis tempemture. As the results of the finest crystallite segregating on sudece and the maxitnum solid solubility of Ir and Ta component in deposits, the coatings with the composition of 70%IrO2 +Ta2O5 prepared at 450℃ presented the mdrimutn electrocatalgtic activitg for O2 evolution in 0. 5M H2SO4 solution.UP to 550℃, Ti base suffered to oxidation resulting in decreasing anode conductivity,therefore, coatings performed a low activity.

Mixed B-site ruddlesden-popper phase Sr_(2)(Ru_(x)Ir_(1-x))O_(4) enables enhanced activity for oxygen evolution reaction

Development of high performance electrocatalysts for oxygen evolution reaction (OER) in acidic media remains a challenge for direct water splitting using an electrolyzer.Recently,Ruddlesden-Popper phase Sr_(2)IrO_(4)was discovered to be an efficient OER catalyst because of its unique structure,which consists of layers of both rock salt and perovskite phases simultaneously.In this study,we prepared a series of B-site mixed,Ruddlesden-Popper phase of Sr_(2)(Ru_(x)Ir_(1-x))O_(4) and examined their electrocatalytic properties for OER in acidic media.Through partial substitution of Ru in the B-site of Ruddlesden-Popper phase materials,we achieved much enhanced OER performance for this series of Sr_(2)(Ru_(x)Ir_(1-x))O_(4)electrocatalysts,among which Sr_(2)(Ru_(0.5)Ir_(0.5))O_(4)exhibited the best catalytic activity with a current density of 8.06 m A/cm^(2) at 1.55 V and a Tafel slope of 47 m V/dec.This current density is three times higher than that of Sr_(2)Ir O_(4).The B-site mixed Sr_(2)(Ru_(0.5)Ir_(0.5))O_(4)retained good stability in acidic conditions for>24 h at 10 m A/cm^(2).A range of techniques were used to characterize the crystal and electronic structures of the Sr_(2)(Ru_(x)Ir_(1-x))O_(4)samples.Our data indicate that the improved OER performance can be correlated to the formation of high level of hydroxyl groups and the enhanced overlap between Ir/Ru 4d and O_(2)p orbitals,revealing a new way for the design of efficient OER electrocatalysts by regulating their composition and electronic structures.

Preparation and Properties of IrO_2 Thin Films Grown by Pulsed Laser Deposition Technique

Highly conductive IrO2 thin films were prepared on Si （100） substrates by means of pulsed laser deposition technique from an iridium metal target in an oxygen ambient atmosphere. Emphasis was put on the effect of oxygen pressure and substrate temperature on the structure, morphology and resistivity of IrO2 films. It was found that the above properties were strongly dependent on the oxygen pressure and substrate temperature. At 20 Pa oxygen ambient pressure, pure polycrystalline IrO2 thin films were obtained at substrate temperature in the 300-500℃ range with the preferential growth orientation of IrO2 films changed with the substrate temperature. IrO2 films exhibited a uniform and densely packed granular morphology with an average feature size increasing with the substrate temperature. The room-temperature resistivity variations of IrO2 films correlated well with the corresponding film morphology changes. IrO2 films with the minimum resistivity of （42 ±6）μΩ·cm was obtained at 500℃.

Performance improvement of InGaN/GaN multiple quantum well visible-light photodiodes by optimizing TEGa flow

The performance of an InGaN/GaN multiple quantum well（MQW） based visible-light Schottky photodiode（PD）is improved by optimizing the source flow of TEGa during In Ga N QW growth. The samples with five-pair InGaN/GaN MQWs are grown on sapphire substrates by metal organic chemical vapor deposition. From the fabricated Schottky-barrier PDs, it is found that the smaller the TEGa flow, the lower the reverse-bias leakage is. The photocurrent can also be enhanced by depositing the In GaN QWs with using lower TEGa flow. A high responsivity of 1.94 A/W is obtained at 470 nm and -3-V bias in the PD grown with optimized TEGa flow. Analysis results show that the lower TEGa flow used for depositing In Ga N may lead to superior crystalline quality with improved InGaN/GaN interface, and less structural defects related non-radiative recombination centers formed in the MQWs.

Light-activated nanoclusters with tunable ROS for wound infection treatment

Infected wounds pose a significant clinical challenge due to bacterial resistance, recurrent infections, and impaired healing. Reactive oxygen species (ROS)-based strategies have shown promise in eradicating bacterial infections. However, the excess ROS in the infection site after treatments may cause irreversible damage to healthy tissues. To address this issue, we developed bovine serum albumin-iridium oxide nanoclusters (BSA-IrOx NCs) which enable photo-regulated ROS generation and scavenging using near infrared (NIR) laser. Upon NIR laser irradiation, BSA-IrOx NCs exhibit enhanced photodynamic therapy, destroying biofilms and killing bacteria. When the NIR laser is off, the nanoclusters' antioxidant enzyme-like activities prevent inflammation and repair damaged tissue through ROS clearance. Transcriptomic and metabolomic analyses revealed that BSA-IrOx NCs inhibit bacterial nitric oxide synthase, blocking bacterial growth and biofilm formation. Furthermore, the nanoclusters repair impaired skin by strengthening cell junctions and reducing mitochondrial damage in a fibroblast model. In vivo studies using rat infected wound models confirmed the efficacy of BSA-IrOx NCs. This study presents a promising strategy for treating biofilm-induced infected wounds by regulating the ROS microenvironment, addressing the challenges associated with current ROS-based antibacterial approaches.

4T1 cell membrane-derived biodegradable nanosystem for comprehensive interruption of cancer cell metabolism

Glycolysis inhibition can effectively block the energy supply and interrupt tumorigenesis in many types of cancers.However,when glycolysis is inhibited,tumor cells will break down glutamine as the raw material for the replenishment pathway to maintain the tricarboxylic acid cycle ensuring energy supply,therefore inducing ineffective interruption of metabolic.Herein,we designed glutamine transporter antagonist L-γ-glutamyl-p-nitroanilide(GPNA)loaded and 4T1 cancer cell membrane coated iridium oxide nanoparticles(IrO_(2)-GPNA@CCM)to realize a comprehensive inhibition of tumor energy supply which synergistically mediated by glycolysis and glutamine cycle.IrO_(2)NPs were used to catalyze the O_(2)generation by facilitating the decomposition of endogenous H_(2)O_(2)in tumor cells,which further downregulated the expression of HIF-1αand PI3K/pAKT to interrupt the generation of lactate.Meanwhile,the loaded GPNA was released under NIR irradiation to bind to alanine-serine-cysteine transporter(ASCT2)for glutamine uptake suppression,therefore realizing the comprehensive dysfunction of cell metabolism.Moreover,both in vitro and in vivo results convinced the thorough energy inhibition effect based on Ir O_(2)-GPNA@CCM NPs,which provided an inspiring strategy for future construction of tumor therapeutic regimen.