Efficient and sustainable water electrolysis achieved by excess electron reservoir enabling charge replenishment to catalysts.

Suppressing the oxidation of active-Ir(III) in IrOx catalysts is highly desirable to realize an efficient and durable oxygen evolution reaction in water electrolysis. Although charge replenishment from supports can be effective in preventing the oxidation of IrOx catalysts, most supports have inherently limited charge transfer capability. Here, we demonstrate that an excess electron reservoir, which is a charged oxygen species, incorporated in antimony-doped tin oxide supports can effectively control the Ir oxidation states by boosting the charge donations to IrOx catalysts. Both computational and experimental analyses reveal that the promoted charge transfer driven by excess electron reservoir is the key parameter for stabilizing the active-Ir(III) in IrOx catalysts. When used in a polymer electrolyte membrane water electrolyzer, Ir catalyst on excess electron reservoir incorporated support exhibited 75 times higher mass activity than commercial nanoparticle-based catalysts and outstanding long-term stability for 250 h with a marginal degradation under a water-splitting current of 1 A cm-2. Moreover, Ir-specific power (74.8 kW g-1) indicates its remarkable potential for realizing gigawatt-scale H2 production for the first time.

Unconventional grain growth suppression in oxygen-rich metal oxide nanoribbons.

Nanograined metal oxides are requisite for diverse applications that use large surface area, such as gas sensors and catalysts. However, nanoscale grains are thermodynamically unstable and tend to coarsen at elevated temperatures. Here, we report effective grain growth suppression in metal oxide nanoribbons annealed at high temperature (900°C) by tuning the metal-to-oxygen ratio and confining the nanoribbons. Despite the high annealing temperatures, the average grain size was maintained at ~6 nm, which also retained their structural integrity. We observe that excess oxygen in amorphous tin oxide nanoribbons prevents merging of small grains during crystallization, leading to suppressed grain growth. As an exemplary application, we demonstrate a gas sensor using grain growth­suppressed tin oxide nanoribbons, which exhibited both high sensitivity and unusual long-term operation stability. Our findings provide a previously unknown pathway to simultaneously achieve high performance and excellent thermal stability in nanograined metal oxide nanostructures.

Synergistic Integration of Chemo-Resistive and SERS Sensing for Label-Free Multiplex Gas Detection.

Practical sensing applications such as real-time safety alerts and clinical diagnoses require sensor devices to differentiate between various target molecules with high sensitivity and selectivity, yet conventional devices such as oxide-based chemo-resistive sensors and metal-based surface-enhanced Raman spectroscopy (SERS) sensors usually do not satisfy such requirements. Here, a label-free, chemo-resistive/SERS multimodal sensor based on a systematically assembled 3D cross-point multifunctional nanoarchitecture (3D-CMA), which has unusually strong enhancements in both "chemo-resistive" and "SERS" sensing characteristics is introduced. 3D-CMA combines several sensing mechanisms and sensing elements via 3D integration of semiconducting SnO2 nanowire frameworks and dual-functioning Au metallic nanoparticles. It is shown that the multimodal sensor can successfully estimate mixed-gas compositions selectively and quantitatively at the sub-100 ppm level, even for mixtures of gaseous aromatic compounds (nitrobenzene and toluene) with very similar molecular structures. This is enabled by combined chemo-resistive and SERS multimodal sensing providing complementary information.

Conformation-modulated three-dimensional electrocatalysts for high-performance fuel cell electrodes.

Unsupported Pt electrocatalysts demonstrate excellent electrochemical stability when used in polymer electrolyte membrane fuel cells; however, their extreme thinness and low porosity result in insufficient surface area and high mass transfer resistance. Here, we introduce three-dimensionally (3D) customized, multiscale Pt nanoarchitectures (PtNAs) composed of dense and narrow (for sufficient active sites) and sparse (for improved mass transfer) nanoscale building blocks. The 3D-multiscale PtNA fabricated by ultrahigh-resolution nanotransfer printing exhibited excellent performance (45% enhanced maximum power density) and high durability (only 5% loss of surface area for 5000 cycles) compared to commercial Pt/C. We also theoretically elucidate the relationship between the 3D structures and cell performance using computational fluid dynamics. We expect that the structure-controlled 3D electrocatalysts will introduce a new pathway to design and fabricate high-performance electrocatalysts for fuel cells, as well as various electrochemical devices that require the precision engineering of reaction surfaces and mass transfer.

Controlling hot electron flux and catalytic selectivity with nanoscale metal-oxide interfaces.

Interaction between metal and oxides is an important molecular-level factor that influences the selectivity of a desirable reaction. Therefore, designing a heterogeneous catalyst where metal-oxide interfaces are well-formed is important for understanding selectivity and surface electronic excitation at the interface. Here, we utilized a nanoscale catalytic Schottky diode from Pt nanowire arrays on TiO2 that forms a nanoscale Pt-TiO2 interface to determine the influence of the metal-oxide interface on catalytic selectivity, thereby affecting hot electron excitation; this demonstrated the real-time detection of hot electron flow generated under an exothermic methanol oxidation reaction. The selectivity to methyl formate and hot electron generation was obtained on nanoscale Pt nanowires/TiO2, which exhibited ~2 times higher partial oxidation selectivity and ~3 times higher chemicurrent yield compared to a diode based on Pt film. By utilizing various Pt/TiO2 nanostructures, we found that the ratio of interface to metal sites significantly affects the selectivity, thereby enhancing chemicurrent yield in methanol oxidation. Density function theory (DFT) calculations show that formation of the Pt-TiO2 interface showed that selectivity to methyl formate formation was much larger in Pt nanowire arrays than in Pt films because of the different reaction mechanism.

Highly efficient oxygen evolution reaction via facile bubble transport realized by three-dimensionally stack-printed catalysts.

Despite highly promising characteristics of three-dimensionally (3D) nanostructured catalysts for the oxygen evolution reaction (OER) in polymer electrolyte membrane water electrolyzers (PEMWEs), universal design rules for maximizing their performance have not been explored. Here we show that woodpile (WP)-structured Ir, consisting of 3D-printed, highly-ordered Ir nanowire building blocks, improve OER mass activity markedly. The WP structure secures the electrochemically active surface area (ECSA) through enhanced utilization efficiency of the extended surface area of 3D WP catalysts. Moreover, systematic control of the 3D geometry combined with theoretical calculations and various electrochemical analyses reveals that facile transport of evolved O2 gas bubbles is an important contributor to the improved ECSA-specific activity. The 3D nanostructuring-based improvement of ECSA and ECSA-specific activity enables our well-controlled geometry to afford a 30-fold higher mass activity of the OER catalyst when used in a single-cell PEMWE than conventional nanoparticle-based catalysts.

Thermally assisted nanotransfer printing with sub-20-nm resolution and 8-inch wafer scalability.

Nanotransfer printing (nTP) has attracted considerable attention due to its good pattern resolution, process simplicity, and cost-effectiveness. However, the development of a large-area nTP process has been hampered by critical reliability issues related to the uniform replication and regular transfer printing of functional nanomaterials. Here, we present a very practical thermally assisted nanotransfer printing (T-nTP) process that can easily produce well-ordered nanostructures on an 8-inch wafer via the use of a heat-rolling press system that provides both uniform pressure and heat. We also demonstrate various complex pattern geometries, such as wave, square, nut, zigzag, and elliptical nanostructures, on diverse substrates via T-nTP. Furthermore, we demonstrate how to obtain a high-density crossbar metal-insulator-metal memristive array using a combined method of T-nTP and directed self-assembly. We expect that the state-of-the-art T-nTP process presented here combined with other emerging patterning techniques will be especially useful for the large-area nanofabrication of various devices.

Metallic Woodpile Nanostructures for Femtomolar Sensing of Alzheimer's Neurofilament Lights.

Alzheimer's disease (AD), the most common age-related neurodegenerative disorder, accompanies a massive degradation of neurons including axonal injury. Being an axonal neuron-specific protein, neurofilament light (NfL) is a blood biomarker that reflects the neurodegeneration in AD, but no attempt has been made yet to develop sensing platforms that target NfLs in blood serum or plasma. Here, we report three-dimensional cross-stacked Pt nanowire arrays for the ultrasensitive photoelectrochemical (PEC) detection of NfLs. We constructed a woodpile-like Pt nanowire array (PtWP)-based biocathode by printing multilayer Pt nanowire arrays in an orthogonal configuration and conjugating them with NfL-specific DA2 antibodies. According to our collective electrochemical analyses, the five-layered PtWP electrode modified with DA2 antibodies exhibited high oxygen reduction activities due to the large electrochemical active surface area and the effective electron transfer properties. We have combined the DA2-PtWP biocathode with a water-oxidizing, iron oxyhydroxide-deposited bismuth vanadate (FeOOH/BiVO4) photoanode to assemble a bias-free PEC detection system. Powered by a white-light-emitting diode, the unbiased PEC platform accurately recognizes NfLs in blood plasma with the limit-of-detection of 38.2 fg/mL and limit-of-quantification of 853 fg/mL, which is 40 times lower than the NfL levels in AD patients' blood.

Engineering Nanoscale Interfaces of Metal/Oxide Nanowires to Control Catalytic Activity.

The interfacial effect between a metal catalyst and its various supporting transition metal oxides on the catalytic activity of heterogeneous catalysis has been extensively explored; engineering interfacial sites of metal supported on metal oxide has been found to influence catalytic performance. Here, we investigate the interfacial effect of Pt nanowires (NWs) vertically and alternatingly stacked with titanium dioxide (TiO2) or cobalt monoxide (CoO) NWs, which exhibit a strong metal-support interaction under carbon monoxide (CO) oxidation. High-resolution nanotransfer printing based on nanoscale pattern replication and e-beam evaporation were utilized to obtain the Pt NWs cross-stacked on the CoO or TiO2 NW on the silicon dioxide (SiO2) substrate with varying numbers of nanowires. The morphology and interfacial area were precisely determined by means of atomic force microscopy and scanning electron microscopy. The cross-stacked Pt/TiO2 NW and Pt/CoO NW catalysts were estimated with CO oxidation under 40 Torr CO and 100 Torr O2 from 200 to 240 °C. Higher catalytic activity was found on the Pt/CoO NW catalyst than on Pt/TiO2 NWs and Pt NWs, which indicates the significance of nanoscale metal-oxide interfaces. As the number of nanowire layers increased, the catalytic activity became saturated. Our study demonstrates the interfacial role of nanoscale metal-oxide interfaces under CO oxidation, which has intriguing applications in the smart design of catalytic materials.

Fabrication and Applications of 3D Nanoarchitectures for Advanced Electrocatalysts and Sensors.

For the last few decades, nanoscale materials and structures have been extensively studied and developed, making a huge impact on human sustainability. For example, the introduction of nanostructures has brought substantial development in electrocatalysts and optical sensing applications. However, there are still remaining challenges that need to be resolved to further improve their performance, reliability, and cost-effectiveness. Herein, long-range ordered 3D nanostructures and their design principles are introduced with an emphasis on electrocatalysts for energy conversion and plasmonic nanostructures for optical sensing. Among the various fabrication techniques, sequential solvent-injection-assisted nanotransfer printing is suggested as a practical fabrication platform for tunable long-range ordered 3D nanostructures composed of ultrahigh-resolution building blocks. Furthermore, the importance of understanding and controlling the 3D design parameters is discussed to realize more efficient energy conversion as well as effective surface-enhanced Raman spectroscopy analyses, suggesting new solutions for clean energy and healthcare issues.