Homolytic H2 dissociation for enhanced hydrogenation catalysis on oxides.

The limited surface coverage and activity of active hydrides on oxide surfaces pose challenges for efficient hydrogenation reactions. Herein, we quantitatively distinguish the long-puzzling homolytic dissociation of hydrogen from the heterolytic pathway on Ga2O3, that is useful for enhancing hydrogenation ability of oxides. By combining transient kinetic analysis with infrared and mass spectroscopies, we identify the catalytic role of coordinatively unsaturated Ga3+ in homolytic H2 dissociation, which is formed in-situ during the initial heterolytic dissociation. This site facilitates easy hydrogen dissociation at low temperatures, resulting in a high hydride coverage on Ga2O3 (H/surface Ga3+ ratio of 1.6 and H/OH ratio of 5.6). The effectiveness of homolytic dissociation is governed by the Ga-Ga distance, which is strongly influenced by the initial coordination of Ga3+. Consequently, by tuning the coordination of active Ga3+ species as well as the coverage and activity of hydrides, we achieve enhanced hydrogenation of CO2 to CO, methanol or light olefins by 4-6 times.

Synthesis of a Spatially Confined, Highly Durable, and Fully Exposed Pd Cluster Catalyst via Sequential Site-Selective Atomic Layer Deposition.

Bottom-up synthesis based on site-selective atomic layer deposition is a powerful atomic-scale processing approach to fabricate materials with desired functionalities. Typical selective atomic layer deposition (ALD) can be achieved using selective activation of a growth area or selective deactivation of a protected area. In this work, we explored the site selectivity based on the difference of the inherent surface reactivity between different materials and within the same materials. By sequentially applying two site-selective atomic layer deposition, the ALD Pd catalyst is spatially confined on ALD SnO2 modified h-BN substrate Pd/SnO2/h-BN shows improved catalytic activity and stability due to strong metal-support interactions and spatial confinement. The results reveal that sequential site-selective ALD is a feasible and effective synthesis strategy that provides an attractive path toward designing and developing highly stable catalysts.

Heterogeneous Synergetic Effect of Metal-Oxide Interfaces for Efficient Hydrogen Evolution in Alkaline Solutions.

Water dissociation in alkaline solutions is one of the biggest challenges in hydrogen evolution reactions (HERs). The key is to obtain a catalyst with optimal and balanced OH adsorption energy and H adsorption/H2 desorption energy. Herein, we synthesized a Ni17W3/WO2 catalyst on the Ni foam that optimized the coverage and size of Ni17W3 alloys decorated on the NiWO4/WO2 substrate. Our experiments showed that Ni17W3-NiWO4 interfaces could accelerate water dissociation, and Ni17W3-WO2 interfaces facilitate adsorbed H atoms spillover and H2 desorption. In addition, we applied a suite of characterization techniques to analyze surface evolution processes in catalysts under various cathodic potentials so as to illustrate the competition between chemical oxidation and electrochemical reduction reactions. The results demonstrated that high coverage of large Ni17W3 nanoparticles resulted in a greater stable interface. The two efficient interfaces synergetically promote the Volmer-Tafel reaction. Ni17W3/WO2 catalysts exhibited extraordinary HER activity with a low overpotential of 48 mV at a 10 mA cm-2 current density and a Tafel slope of 33 mV dec-1. This work has shown that low-cost catalysts with proper hierarchical interfaces can be engineered and can be optimized into a tandem system, which will significantly promote HER activity in alkaline electrolytes.

A Performance-Enhanced Liquid Metal-Based Microheater with Parallel Ventilating Side-Channels.

Gallium-based liquid metal can be used as a material for microheaters because it can be easily filled into microchannels and electrified to generate Joule heat, but the liquid metal-based microheater will suffer breakage induced by voids forming within the liquid metal when the temperature normally gets higher than 100 °C. To resolve this problem, a novel liquid metal-based microheater with parallel ventilating side-channels is presented. It consists of a liquid-metal heating channel and two parallel ventilating side-channels. The heating channel is connected with the side-channels by small gaps between polydimethylsiloxane (PDMS) posts. Experimental results show that this novel microheater can be heated up to 200 °C without damage. To explain its excellent performance, an experiment is performed to discover the development of the voids within the liquid-metal heating channel, and two reasons are put forward in this work on the basis of the experiment. Afterward pressing and bending tests are conducted to explore the mechanical stability of the novel microheaters. Finally, the microheaters are applied to warm water to show their good flexibility on non-flat surfaces. In consequence, the novel liquid metal-based microheater is believed to be widely applicable to soft micro-electro-mechanical system(MEMS) heating devices.

A Liquid-Metal-Based Dielectrophoretic Microdroplet Generator.

This paper proposes a novel microdroplet generator based on the dielectrophoretic (DEP) force. Unlike the conventional continuous microfluidic droplet generator, this droplet generator is more like "invisible electric scissors". It can cut the droplet off from the fluid matrix and modify droplets' length precisely by controlling the electrodes' length and position. These electrodes are made of liquid metal by injection. By applying a certain voltage on the liquid-metal electrodes, the electrodes generate an uneven electric field inside the main microfluidic channel. Then, the uneven electric field generates DEP force inside the fluid. The DEP force shears off part from the main matrix, in order to generate droplets. To reveal the mechanism, numerical simulations were performed to analyze the DEP force. A detailed experimental parametric study was also performed. Unlike the traditional droplet generators, the main separating force of this work is DEP force only, which can produce one droplet at a time in a more precise way.

Stretchable Pressure Sensor with Leakage-Free Liquid-Metal Electrodes.

Nowadays, with the development of wearable devices, stretchable pressure sensors have been widely adopted in all kinds of areas. Most of the sensors aim to detect small pressure, such as fingertip tactile sensing, but only a few are focused on high-pressure sensing, such as foot pressure sensing during men's walking. In this work, a liquid metal-based stretchable sensor for large-pressure measurement is investigated. This sensor is fully stretchable because it is made of soft materials. However, when the soft sensor is subjected to high pressure, the liquid metal easily leaks from microchannels because it maintains the liquid state at room temperature. We therefore propose to fabricate liquid metal-based leakage-free electrodes to handle the liquid-metal leak. Parametric studies are conducted to compare this sensor with liquid-metal-only electrodes and leakage-free electrodes. The leakage-free electrodes increase the measurement ranges from 0.18, 0.18, and 0.15 MPa to 0.44 MPa, with higher linearity and precision. The improvement in the liquid-metal electrode enables the sensors to work stably within 0.44 MPa pressure and 20% strain. In addition, we integrate two capacitors, namely, a working capacitor and a reference capacitor, into one sensor to reduce the influence of parasitic capacitance brought about by external interference. This stretchable capacitive sensor capable of working under a wide range of pressure with good repeatability, sensitivity, and linearity, exhibits great potential use for wearable electronics. Finally, the method for fabricating leakage-free electrodes shows great value for hyperelastic electronics manufacturing and micromachine technology.

A liquid metal based capacitive soft pressure microsensor.

A liquid-metal based capacitive soft pressure microsensor is proposed in this work for measuring pressure in microchannels. To measure the pressure of the target microchannel, a short detection channel is fabricated and connected to the target microchannel. Because the detection channel has only one outlet at the end which is connected to the target microchannel, the fluid in the detection channel will stay still during the measurement and the pressure remains constant inside the detection channel. A segment of reference fluid which is immiscible with the working fluid is sealed inside the detection channel. Because the chip material is soft, the pressure change will lead to the movement of the interface between the reference fluid and working fluid inside the detection channel. A pair of liquid metal electrodes are fabricated on both sides of the detection channel. By measuring the capacitance between these two liquid metal electrodes, the movement of the interface can be detected, and thus the pressure change can be detected as well. To minimize the influence from the environment, two liquid metal shield layers are placed on the top and the bottom of the microchannel layer separately. The microsensor was first tested in a microfluidic system and then utilized to measure the blood pressure of rabbit carotid artery in vivo. The experimental results showed excellent stability and linear correlation between capacitance and the value of fluid pressure. The pressure sensor can achieve a resolution of 7.5 mmHg within a pressure range of 20-300 mmHg. This work provides a promising approach to develop an implantable blood or intraocular pressure-monitoring device for clinical use.

A Handy Flexible Micro-Thermocouple Using Low-Melting-Point Metal Alloys.

A handy, flexible micro-thermocouple using low-melting-point metal alloys is proposed in this paper. The thermocouple has the advantages of simple fabrication and convenient integration. Bismuth/gallium-based mixed alloys are used as thermocouple materials. To precisely inject the metal alloys to the location of the sensing area, a micro-polydimethylsiloxane post is designed within the sensing area to prevent outflow of the metal alloy to another thermocouple pole during the metal-alloy injection. Experimental results showed that the Seebeck coefficient of this thermocouple reached -10.54 µV/K, which was much higher than the previously reported 0.1 µV/K. The thermocouple was also be bent at 90° more than 200 times without any damage when the mass ratio of the bismuth-based alloy was <60% in the metal-alloy mixture. This technology mitigated the difficulty of depositing traditional thin⁻film thermocouples on soft substrates. Therefore, the thermocouple demonstrated its potential for use in microfluidic chips, which are usually flexible devices.

A Handy Liquid Metal Based Non-Invasive Electrophoretic Particle Microtrap.

A handy liquid metal based non-invasive particle microtrap was proposed and demonstrated in this work. This kind of microtrap can be easily designed and fabricated at any location of a microfluidic chip to perform precise particle trapping and releasing without disturbing the microchannel itself. The microsystem demonstrated in this work utilized silicon oil as the continuous phase and fluorescent particles (PE-Cy5, SPHEROTM Fluorescent Particles, BioLegend, San Diego, CA, USA, 10.5 µm) as the target particles. To perform the particle trapping, the micro system utilized liquid-metal-filled microchannels as noncontact electrodes to generate different patterns of electric field inside the fluid channel. According to the experimental results, the target particle can be selectively trapped and released by switching the electric field patterns. For a better understanding the control mechanism, a numerical simulation of the electric field was performed to explain the trapping mechanism. In order to verify the model, additional experiments were performed and are discussed.

Unidirectional Droplet Transport on the Biofabricated Butterfly Wing.

Water droplet unidirectional transport on the asymmetric superhydrophobic surface has attracted much interest in theory analysis and applications, such as self-cleaning, antifogging, anti-icing, heat transfer, and so on. Different from the symmetrical performance on the uniform topographies, the droplets acting on the asymmetric surface exhibit an anisotropic state and easily roll off the surface along the special direction. This phenomenon is indicated by natural butterfly wings. The flexible asymmetrically arranged microstep induces the droplet to release along the outside radial (RO) direction and to pin against the RO direction. Here, inspired by butterfly wings, a kind of surface for superhydrophobic and unidirectional droplet transport is achieved by integrating the methods of soft lithography and enhanced crystal growth. The water droplet shows the anisotropic state on the biofabricated surface, and it rolls off easily along the step direction. The droplet is unidirectionally driven off the surface by the asymmetric surface tension force generated by the microstep topography. This experiment is significant for designing self-cleaning surfaces.