Nanoporous Substrates Research Articles

Electroless Plating of Nanoporous Substrates for Thin Film-Solid Oxide Fuel Cells

Thin-film solid oxide fuel cells (TF-SOFCs) are an attractive renewable energy source due to their high efficiency, increased power output and ability to be efficiently stacked for power generation at a small or large-scale. [N. Q. Minh, J Am Ceram Soc. 1993; 76(3):563-588.] Nanoporous Al2O3, also known as anodized aluminum oxide (AAO) is an appropriate substrate for TF-SOFCs due to its high temperature stability, chemically inert nature, and porosity that allows gas flow to the anode. The aligned, nano-sized pores allow for both conformal sputtering on the surface and efficient fuel delivery to the anode, making it particularly suited for thin film deposition. Electroless nickel plating is used to achieve a fully conductive, nanoporous substrate which catalyzes the hydrogen oxidation reaction and improves current collection efficiency in TF-SOFCs. A minimum plating temperature of 60°C is needed to grow nanoscale Ni deposits into a conductive film without compromising the porosity of the surface. Effective stirring methods are used to deliver the plating solution throughout the high-aspect ratio pores of the AAO substrate and create thru-plane conductivity. To achieve conformal plating, the number of pre-treatment steps was optimized to prevent overplating and create a homogenous Ni deposit. Finally, with the creation of a conformally coated, conductive porous substrate, we can improve the efficiency and power output of TF-SOFC performance with commercially relevant active areas (larger than 1 cm2).

A Scalable Synthesis of Ag Nanoporous Film As an Efficient SERS-Substrates for Sensitive Detection of Nanoplastics.

Nanoplastics pollution has led to a severe environmental crisis because of a large accumulation of these smaller nanoplastic particles in the aquatic environment and atmospheric conditions. Detection of these nanoplastics is crucial for food safety monitoring and human health. In this work, we report a simple and eco-friendly method to prepare a SERS-substrate-based nanoporous Ag nanoparticle (NP) film through vacuum thermal evaporation onto a vacuum-compatible deep eutectic solvent (DES) coated growth substrate for quantitative detection of nanoplastics in environmental samples. The nanoporous Ag NP films with controlled pores were achieved by the soft-templating role of DESs over the growth substrate, which enabled the self-assembly of deposited Ag NPs over the surface of DES. The optimized nanoporous Ag substrate provides high sensitivity in the detection of analyte molecules, crystal violet (CV), and rhodamine 6G (R6G) with a limit of detection (LOD) up to 1.5 × 10-13 M, excellent signal reproducibility, and storage stability. Moreover, we analyzed quantitative SERS detection of polyethene terephthalate (PET, size of 200 nm) and polystyrene (PS, size of 100 nm) nanoplastics with an LOD of 0.38 and 0.98 μg/mL, respectively. In addition, the SERS substrate efficiently detects PET and PS nanoplastics in real environmental samples, such as tap water, lake water, and diluted milk. The enhanced SERS sensing ability of the proposed nanoporous Ag NP film substrate holds immense potential for the sensitive detection of various nanoplastic contaminants present in environmental water.

Synthesis and mechanism of hierarchical porous Ag/CuxO (x = 1, 2) nanowire hybrids for high photocatalytic degradation

To improve organic pollutant degradation ability, this work aims at designing a novel porous Cu-Ag bimetal hybrid with unique architecture, fertile porosity as well as Schottky junction. Herein, a free-standing hybrid with Ag nanoparticles modified CuxO (x = 1, 2) nanowires in-situ grown on the nanoporous Cu-Ag bimetal network (Ag/CuxO@NP-CuAg) was successfully synthesized by dealloying and then anodizing process. Compared with monometallic CuxO nanowires integrated with nanoporous Cu substrate (CuxO@NPC), the Ag/CuxO@NP-CuAg hybrids with the Ag/CuxO Schottky junction and SPR effect of Ag nanoparticles, are favorable to accelerate the transportation of photo-generated carriers and avoid the recombination of electrons (e-) and holes (h+), thus exhibiting the enhanced photocatalytic performance for RhB. Such remarkable performance is also contributed to the multimodal hierarchical porous structure and the integration design strategy. Moreover, by density functional theory (DFT) calculation, a typical Z-scheme mechanism is proposed to better understand the photocatalytic degradation process. The formation mechanism of the Ag/CuxO nanowires is also investigated.

Two-axis beamsteering using a wideband Butler matrix and series-fed arrays for millimeter wave frequencies fabricated on metallic-nanowire-membrane platform

This work presents a two-axis beamsteering system designed for WLAN millimeter-wave frequencies. The system comprises a wideband Butler matrix and series-fed arrays. The Butler matrix, implemented with microstrip lines, features a wideband crossover with low phase imbalance, enabling four discrete beamsteering directions on the radiation H-plane. The series-fed arrays enable frequency-dependent beamsteering on the E-plane. The entire system was fabricated on a nanoporous alumina substrate using metallic-nanowire-membrane technology. Measurement results indicate an impedance bandwidth of 17.71%, which accommodates typical requirements for 60 GHz WLAN applications. Additionally, beamsteering in the desired directions was achieved. The presented Butler matrix structure stands out as one of the most compact found in the reviewed literature. The produced device successfully balances wideband behavior, compactness, and fabrication simplicity.

Nanoporous Gold Thin Films as Substrates to Analyze Liquids by Cryo-atom Probe Tomography.

Cryogenic atom probe tomography (cryo-APT) is being developed to enable nanoscale compositional analyses of frozen liquids. Yet, the availability of readily available substrates that allow for the fixation of liquids while providing sufficient strength to their interface is still an issue. Here, we propose the use of 1-2-µm-thick binary alloy film of gold-silver sputtered onto flat silicon, with sufficient adhesion without an additional layer. Through chemical dealloying, we successfully fabricate a nanoporous substrate, with an open-pore structure, which is mounted on a microarray of Si posts by lift-out in the focused-ion beam system, allowing for cryogenic fixation of liquids. We present cryo-APT results obtained after cryogenic sharpening, vacuum cryo-transfer, and analysis of pure water on the top and inside the nanoporous film. We demonstrate that this new substrate has the requisite characteristics for facilitating cryo-APT of frozen liquids, with a relatively lower volume of precious metals. This complete workflow represents an improved approach for frozen liquid analysis, from preparation of the films to the successful fixation of the liquid in the porous network, to cryo-APT.

Induced Formation of Plasma Membrane Protrusions with Porous Materials as Instructive Surfaces.

The plasma membrane is a vital component in cellular processes, and its structure has a significant impact on cellular behavior. The physical characteristics of the extracellular environment, along with the presence of surface pores, can influence the formation of membrane protrusions. Nanoporous surfaces have demonstrated their capacity to induce membrane protrusions in both adherent and non-adherent cells. This chapter presents a methodology that utilizes a nanoporous substrate with nanotopographical constraints to effectively stimulate the formation of membrane protrusions in cells.

(Invited) Making Nanostructured Composites Via Inner-Pore Electrodeposition into Nanoporous Metals

The selective removal of Ag from a solid solution of Ag-Au or Ag-Au-Pt yields a 3D bicontinuous, open-pore, nanoporous gold substrate (NPG), that is rich in the more noble metal(s)1 (Au and/or Pt). NPG has been successfully developed by the intelligent use of the conventionally-undesired dealloying corrosion. The excellent properties of NPG are attributed to the surface area-to-volume ratio, and high curvature of nanoligament surfaces2,3 . While a lot of recent research has been focusing on the structure/property relationships of NPG as a functional material in its own right4,5, the further use of NPG as a sophisticated template for fabricating complex nanostructured materials is worthy of attention.Previous work on atom probe tomography characterization of NPG6,7 showed the successful inner-pore electrodeposition of a fully compact Cu support, thus, opening the door to implementing that newly developed method to the creation of finely tuned nanostructures, using NPG as a template. Fabrication of functional nanostructures pertaining to the interests of the catalysis and mechanics communities will be demonstrated through the electrodeposition of Cu and Co on NPG. Key aspects that enable this unexpected complete infiltration of NPG layer will be highlighted including, a characteristic "subpotential" curvature-driven electrodeposition regime8. Insights on the associated electrodeposition mechanisms are gained through the pairing of electrochemical methods and high-resolution characterization techniques. Furthermore, recent advances in structural and chemical modifications that increase the complexity and tunability of NPG-based nanocomposites will be discussed for the first time. References Newman, R. C. 2.05 - Dealloying. in Shreir’s Corrosion (eds. Cottis, B. et al.) 801–809 (Elsevier, 2010).Zielasek, V. et al. Gold Catalysts: Nanoporous Gold Foams. Angewandte Chemie International Edition 45, 8241–8244 (2006).Xue, Y., Markmann, J., Duan, H., Weissmüller, J. & Huber, P. Switchable imbibition in nanoporous gold. Nature Communications 5, (2014).Wittstock, A., Wichmann, A., Biener, J. & Bäumer, M. Nanoporous gold: A new gold catalyst with tunable properties. Faraday Discuss (2011) doi:10.1039/c1fd00022e.Li, X. et al. Nanoporous-Gold-Based Hybrid Cantilevered Actuator Dealloyed and Driven by A Modified Rotary Triboelectric Nanogenerator. Sci Rep (2016) doi:10.1038/srep24092.El-Zoka, A. A., Langelier, B., Botton, G. A. & Newman, R. C. Enhanced analysis of nanoporous gold by atom probe tomography. Mater Charact 128, (2017).El-Zoka, A. A., Langelier, B., Korinek, A., Botton, G. A. & Newman, R. C. Nanoscale mechanism of the stabilization of nanoporous gold by alloyed platinum. Nanoscale 10, (2018).Lee, L., He, D., Carcea, A. G. & Newman, R. C. Exploring the reactivity and nanoscale morphology of de-alloyed layers. Corros Sci 49, 72–80 (2007).

Fabrication of SERS substrates by laser restructuring of interconnected Au nanostructures for urea detection

We discuss a facile, fast, simple, and reproducible fabrication method to modulate the structural morphology of the SERS substrate to improve its performance. The interconnected Au network structure named as nanoporous Au (NP–Au) is prepared by the dealloying method and further exposed with varied laser power in order to check the effect of power variation on the morphology as well as on the SERS performance. The effectiveness of the substrate has been tested by detecting Rhodamine 6G as a probe molecule. The Raman results show a good linear relationship with the laser power increment up to 3.2 mW and after that, the signal becomes saturated for a further increment in the power. The substrate is able to enhance the signal up to 102-fold as well able to show all the characteristic peaks without any damage to the probe molecule. Morphological identification reveals that different sizes and shapes of the pores (open, diffused, and interlinked) are responsible for the SERS signal enhancement. Subsequently, the sensitivity of SERS substrate has been examined and the result suggested that the optimal concentration of Rhodamine is 10−9 M. Furthermore, the substrate possesses good uniformity by representing a relative standard deviation value of less than 15 %. The substrate potential for real-world application has been examined by identifying urea (pesticide) molecules. The prepared nanoporous substrate is able to show a well-intensified signal with ∼16-fold enhancement compared to planar Silicon substrate.

Unusual effects of a nanoporous gold substrate on cell adhesion and differentiation because of independent multi-branch signaling of focal adhesions

A variety of cell behaviors, such as cell adhesion, motility, and fate, can be controlled by substrate characteristics such as surface topology and chemistry. In particular, the surface topology of substrates strongly affects cell behaviors, and the topological spacing is a critical factor in inducing cell responses. Various works have demonstrated that cell adhesion was enhanced with decreasing topological spacing although differentiation progressed slowly. However, there are exceptions, and thus, correlations between topological spacing and cell responses are still debated. We show that a nanoporous gold substrate affected cell adhesion while it neither affected osteogenic nor adipogenic differentiation. In addition, the cell adhesion was reduced with decreasing pore size. These do not agree with previous findings. A focal adhesion (FA) is an aggregate of modules comprising specific proteins such as FA kinase, talin, and vinculin. Therefore, it is suggested that because various extracellular signals can be independently branched off from the FA modules, the unusual effects of nanoporous gold substrates are related to the multi-branching of FAs.Graphical

Adhesion and morphology of mammalian cells on nanoporous and nonporous spherical carbon substrates

Three spherical activated carbons (SACs) were used as substrates for mammalian cell proliferation. SACs were obtained by carbonizing styrene-co-divinylbenzene ion exchangers 35WET, XAD4, or 1200H. The new materials (XAD_C, WET_C, and H_C) were characterized by adsorption–desorption nitrogen isotherms and mercury intrusion porosimetry. XAD_C and WET_C exhibited well-developed BET surface areas, similar total pore volumes, and highly different pore size distributions. H_C was nonporous spherical material—reference material. The XAD_C was meso-macroporous, but the WET_C was micro-mesoporous. All SACs were not cytotoxic toward Leydig TM3 cells. The differences in porous structure and morphology of the carbon scaffolds led to morphological differences in adhered cells. The monolayer of cells was distributed flat over the entire WET_C and H_C surfaces. Leydig TM3 cells adhered to nonporous SAC but were easily washed out due to weak adhesion. The cells adhered in clusters to XAD_C and proliferated in clusters. As microscopic techniques and viability tests demonstrated, only nanoporous carbons provided a good surface for the attachment and proliferation of eukaryotic cells.

Fully Integrated 3D Microelectrode Arrays with Polydopamine-Mediated Silicon Dioxide Insulation for Electrophysiological Interrogation of a Novel 3D Human, Neural Microphysiological Construct.

Advances within in vitro biological system complexity have enabled new possibilities for the "Organs-on-a-Chip" field. Microphysiological systems (MPS) as such incorporate sophisticated biological constructs with custom biological sensors. For microelectromechanical systems (MEMS) sensors, the dielectric layer is critical for device performance, where silicon dioxide (SiO2) represents an excellent candidate due to its biocompatibility and wide utility in MEMS devices. Yet, high temperatures traditionally preclude SiO2 from incorporation in polymer-based BioMEMS. Electron-beam deposition of SiO2 may provide a low-temperature, dielectric serving as a nanoporous MPS growth substrate. Herein, we enable improved adherence of nanoporous SiO2 to polycarbonate (PC) and 316L stainless steel (SS) via polydopamine (PDA)-mediated chemistry. The resulting stability of the combinatorial PDA-SiO2 film was interrogated, along with the nature of the intrafilm interactions. A custom polymer-metal three-dimensional (3D) microelectrode array (3D MEA) is then reported utilizing PDA-SiO2 insulation, for definition of novel dorsal root ganglion (DRG)/nociceptor and dorsal horn (DH) 3D neural constructs in excess of 6 months for the first time. Spontaneous/evoked compound action potentials (CAPs) are successfully reported. Finally, inhibitory drugs treatments showcase pharmacological responsiveness of the reported multipart biological activity. These results represent the initiation of a novel 3D MEA-integrated, 3D neural MPS for the long-term electrophysiological study.

Electrodeposition of silicon films from organic solvents on nanoporous copper substrates

Electrodeposition of silicon films from organic solvents on nanoporous copper substrates

Anti-Icing Mechanism for a Novel Slippery Aluminum Stranded Conductor.

The icing of transmission conductor seriously threatens the safe operation of power grids. Slippery lubricant-infused porous surface (SLIPS) has shown great potential for anti-icing applications. However, aluminum stranded conductors have complex surfaces, and the current SLIPSs are almost prepared and studied on small flat plates. Herein, the construction of SLIPS on the conductor was realized through anodic oxidation and the anti-icing mechanism of the slippery conductor was studied. Compared to the untreated conductor, the SLIPS-conductor reduces the icing weight by 77% in the glaze icing test and shows very low ice-adhesion strength (7.0 kPa). The excellent anti-icing performance of the slippery conductor is attributed to the droplet impact dynamics, icing delay, and lubricant stability. The dynamic behavior of water droplets is most affected by the complex shape of the conductor surface. Specifically, the impact of the droplet on the conductor surface is asymmetric and the droplet can slide along the depression in low-temperature and high-humidity environments. The stable lubricant of SLIPS increases both the nucleation energy barriers and the heat transfer resistance, which greatly delays the freezing time of droplets. Besides, the nanoporous substrate, the compatibility of the substrate with the lubricant, and the lubricant characteristics contribute to the lubricant stability. This work provides theoretical and experimental guidance on anti-icing strategies for transmission lines.

Wearable and Flexible Nanoporous Surface-Enhanced Raman Scattering Substrates for Sweat Enrichment and Analysis

Surface-enhanced Raman spectroscopy (SERS), with high sensitivity to a broad range of molecules, can detect molecular “fingerprints” in a complex substance and thereby offers a promising solution for noninvasive medical diagnostics and personal healthcare monitoring. The eventual realization of such applications relies on SERS substrates with dense and uniform hot spots, good chemical stability, and high mechanical durability. With these criteria in mind, we developed a flexible nanoporous SERS substrate via the in situ synthesis of gold nanostars (AuNSs) on an ion-track-etched polycarbonate membrane. The nanoporous SERS substrate can realize analyte enrichment and exhibit excellent Raman performance by taking the advantage of hot spots on AuNSs. The SERS substrate yields highly repeatable and uniform signals for analytes (e.g., methylene blue) over a wide concentration range from 10–4 to 10–13 M. The flexible SERS substrate even can work well after 2000 times bending and exhibit excellent stability for long-term use. It can be prepared on a large scale with a low-cost and simple fabrication process and can be used repeatedly after cleaning to reduce the use-cost further. On-body experiments prove that the sweat SERS substrate allows effective identification of sweat contents, such as lactic acid and uric acid (UA), and the monitoring of diet-induced variation in sweat UA. The potential of the wearable nanoporous SERS substrates in sweat analysis thus has been demonstrated, opening possibilities for autonomous and noninvasive medical health monitoring.

Spatio-temporal programming of lyotropic phase transition in nanoporous microfluidic confinements

HypothesisThe nanoporous polydimethylsiloxane (PDMS) surfaces of a rectangular microfluidic channel, selectively uptakes water molecules, concentrating the solute molecules in an aqueous phase, that could drive phase transitions. Factors such as surface wettability, channel geometry, the surface-to-volume ratio, and surface topography of the confinements could play a key role in tuning the phase transitions spatio-temporally. ExperimentsUsing a lyotropic chromonic liquid crystal as model biological material, confined within nanoporous microfluidic environments, we study molecular assembly driven by nanoporous substrates. By combining timelapse polarized imaging, quantitative image processing, and a simple mathematical model, we analyze the phase transitions and construct a master diagram capturing the role of surface wettability, channel geometry and embedded topography on programmable lyotropic phase transitions. FindingsIntrinsic PDMS nanoporosity and confinement cross-section, together with the imposed wettability regulate the rate of the N-M phase transition; whereas the microfluidic geometry and embedded topography enable phase transition at targeted locations. We harness the emergent long-range order during N-M transition to actuate elasto-advective transport of embedded micro-cargo, demonstrating particle manipulation concepts governed by tunable phase transitions. Our results present a programmable physical route to material assembly in microfluidic environment, and offer a new paradigm for assembling genetic components, biological cargo, and minimal synthetic cells.

Electrical Conductivity and Photodetection in 3D‐Printed Nanoporous Structures via Solution‐Processed Functional Materials

Abstract3D‐printed conductive structures are highly attractive due to their great potential for customizable electronic devices. While the traditional 3D printing of metal requires high temperatures to sinter metal powders or polymer/metal composites, low or room temperature processes will be advantageous to enable multi‐material deposition and integration of optoelectronic applications. Herein, digital light processing technology and inkjet printing are combined as an effective strategy to fabricate customized 3D conductive structures. In this approach, a 3D‐printed nanoporous (NPo) polymeric material is used as a substrate onto which a nanoparticle‐based Ag ink is printed. SEM and X‐ray nano computed tomography (nanoCT) measurements show that the porous morphology of the pristine NPo is retained after deposition and annealing of the Ag ink. By optimizing the deposition conditions, conductive structures with sheet resistance <2 Ω sq−1 are achieved when annealing at temperatures as low as 100 °C. Finally, the integration of an inkjet‐printed photodetector is investigated based on an organic semiconductor active layer onto the NPo substrate. Thus, the potential of this approach is demonstrated for the additive manufacturing of functional 3D‐printed optoelectronic devices.

Thin film liquid-vapor phase change phenomena over nano-porous substrates: A molecular dynamics perspective

Surfaces with nano-pores have significant effect in enhancing heat transfer during phase change process. In this study, Molecular dynamics simulations have been performed to investigate thin film evaporation over different nano-porous substrate. The molecular system consists of argon as the working fluid and Platinum as the solid substrate. To study the effect of the nano-pores in phase change process, the nano-porous substrates had been structured with four different hexagonal porosity with three different heights. The structures of the hexagonal nano-pore were characterized through variation of void fraction as well as height to arm thickness ratio. Qualitative heat transfer performance has been characterized by closely monitoring the temporal variation of temperature and pressure, net evaporation number, wall heat flux of the system for all cases under consideration. The quantitative characterization of heat and mass transfer performance has been done by calculating the average heat flux and evaporative mass flux. Diffusion coefficient of argon is also evaluated to illustrate the effect of these nano-porous substrate in enhancing the movement of argon atoms thus heat transfer. It has been found that the presence of hexagonal nano-porous substrates significantly increases heat transfer performance. Structures with lower void fraction offers better enhancement of heat flux and other transport characteristics. Increment in nano-pores height also significantly enhances heat transfer. Present study clearly points out the noteworthy role associated with nano-porous substrate in modulating heat transfer characteristics during liquid-vapor phase change phenomena both from qualitative and quantitative perspectives.

Hydrophobic-oleophilic surfaces based on chemical modification of nanoporous alumina

Hydrophobic/oleophilic nanoporous anodic alumina substrates were fabricated by two-step anodization method following of chemical modification with 1H, 1H, 2H, 2H-perfluorooctyltrichlorosilane (FOTS). Surface morphology was characterized using a scanning electron microscopy. The influence of the topography and the pore size of the surface in the contact angle measurements with different solvents have been studied. The water repellence capacity of the nanoporous anodic alumina structure as fabricated depends on pore diameter but, there is a critical value of pore size beyond which the water contact angle decrease. After chemical modification of the surface, this effect is not observed. The porous topography of the material is not an advantage for the oleophibicity. The CA values for the non-porous surface using different solvents are lower than the structured surface.The results obtained in this study can be used to desire wettability properties. Modified NAA exhibit hydrophobicity and at the same time permeability for solvents with low surface tension.

Functional Ultrathin Separators Proactively Stabilizing Zinc Anodes for Zinc-Based Energy Storage.

Ultrathin separators are indispensable to high-energy-density zinc-ion batteries (ZIBs), but their easy failure caused by zinc dendrites poses a great challenge. Herein, 23µm-thick functional ultrathin separators (FUSs), realizing superb electrochemical stability of zinc anodes and outstanding long-term durability of ultrathin separators, are reported. In the FUSs, an ultrathin but mechanically strong nanoporous membrane substrate benefits fast and flux-homogenized Zn2+ transport, while a metal-organicframework(MOF)-derived C/Cu nanocomposite decoration layer provides rich low-barrier zinc nucleation sites, thereby synergistically stabilizing zinc anodes to inhibit zinc dendrites and dendrite-caused separator failure. Investigation of the zinc affinity of the MOF-derived C/Cu nanocomposites unravels the high zincophilicity of heteroatom-containing C/Cu interfaces. Zinc anodes coupled with the FUSs present superior electrochemical stability, whose operation lifetime exceeds 2000h at 1mA cm-2 and 600h at 10mA cm-2 , 40-50 times longer than that of the zinc anodes using glass-fiber separators. The reliability of the FUSs in ZIBs and zinc-ion hybrid supercapacitors is also validated. This work proposes a new strategy to stabilize zinc anodes and provides theoretical guidance in developing ultrathin separators for high-energy-density zinc-based energy storage.

Vapor Phase Dealloying Derived Nanoporous Co@CoO/RuO2 Composites for Efficient and Durable Oxygen Evolution Reaction

AbstractThe development of low‐cost and effective oxygen evolution reaction (OER) electrocatalysts to expedite the slow kinetics of water splitting is crucial for increasing the efficiency of energy conversion from electricity to hydrogen fuel. Herein, 3D bicontinuous nanoporous Co@CoO/RuO2 composites with tunable sizes and chemical compositions are fabricated by introducing vapor phase dealloying of cobalt‐based alloys. The influence of physical parameters on the formation of nanoporous Co substrates with various feature ligament sizes is systematically investigated. The CoO/RuO2 shell is constructed by integrating a thin layer of RuO2 on the inner surface of nanoporous Co, where the CoO interlayer is formed by annealing oxidization. The composite catalyst delivers an ultralow overpotential of 198 mV at 10 mA cm−2, Tafel slope of 57.1 mV dec−1, and long‐term stability of 50 h. The superior OER activity and fast reaction kinetics are attributed to charge transfer through the coupling of CoORu bonds at the interface and the excellent nanopore connectivity, while the durability originates from the highly stable CoO/RuO2 interface.