Ternary Alloys Enable Efficient Production of Methoxylated Chemicals via Selective Electrocatalytic Hydrogenation of Lignin Monomers.

We explore the selective electrocatalytic hydrogenation of lignin monomers to methoxylated chemicals, of particular interest, when powered by renewable electricity. Prior studies, while advancing the field rapidly, have so far lacked the needed selectivity: when hydrogenating lignin-derived methoxylated monomers to methoxylated cyclohexanes, the desired methoxy group (-OCH3) has also been reduced. The ternary PtRhAu electrocatalysts developed herein selectively hydrogenate lignin monomers to methoxylated cyclohexanes-molecules with uses in pharmaceutics. Using X-ray absorption spectroscopy and in situ Raman spectroscopy, we find that Rh and Au modulate the electronic structure of Pt and that this modulating steers intermediate energetics on the electrocatalyst surface to facilitate the hydrogenation of lignin monomers and suppress C-OCH3 bond cleavage. As a result, PtRhAu electrocatalysts achieve a record 58% faradaic efficiency (FE) toward 2-methoxycyclohexanol from the lignin monomer guaiacol at 200 mA cm-2, representing a 1.9× advance in FE and a 4× increase in partial current density compared to the highest productivity prior reports. We demonstrate an integrated lignin biorefinery where wood-derived lignin monomers are selectively hydrogenated and funneled to methoxylated 2-methoxy-4-propylcyclohexanol using PtRhAu electrocatalysts. This work offers an opportunity for the sustainable electrocatalytic synthesis of methoxylated pharmaceuticals from renewable biomass.

Nature-Inspired Structural Materials for Flexible Electronic Devices.

Exciting advancements have been made in the field of flexible electronic devices in the last two decades and will certainly lead to a revolution in peoples' lives in the future. However, because of the poor sustainability of the active materials in complex stress environments, new requirements have been adopted for the construction of flexible devices. Thus, hierarchical architectures in natural materials, which have developed various environment-adapted structures and materials through natural selection, can serve as guides to solve the limitations of materials and engineering techniques. This review covers the smart designs of structural materials inspired by natural materials and their utility in the construction of flexible devices. First, we summarize structural materials that accommodate mechanical deformations, which is the fundamental requirement for flexible devices to work properly in complex environments. Second, we discuss the functionalities of flexible devices induced by nature-inspired structural materials, including mechanical sensing, energy harvesting, physically interacting, and so on. Finally, we provide a perspective on newly developed structural materials and their potential applications in future flexible devices, as well as frontier strategies for biomimetic functions. These analyses and summaries are valuable for a systematic understanding of structural materials in electronic devices and will serve as inspirations for smart designs in flexible electronics.

Supramolecular hydrogels for antimicrobial therapy.

The emergence of drug-resistant microbes has become a threat to global health, and microbial infections severely limit the use of healthcare materials. To achieve efficient antimicrobial therapy, supramolecular hydrogels demonstrate unprecedented advantages in medical applications due to the tunable and reversible nature of their supramolecular interactions and the capability of hydrogels to incorporate various therapeutic agents. Herein, antimicrobial hydrogels are categorized according to their inherent antimicrobial properties or based on their roles in encapsulating antimicrobial materials. Moreover, strategies to further enhance the antimicrobial efficacy of hydrogels are highlighted, such as the incorporation of antifouling agents or the enabling of response towards physiological cues. We envision that supramolecular hydrogels, in combination with modern medical technology and devices, will contribute to the development of efficient and safe systems for antimicrobial therapy.

Approaching the Lithiation Limit of MoS2 While Maintaining Its Layered Crystalline Structure to Improve Lithium Storage.

MoS2 holds great promise as high-rate electrode for lithium-ion batteries since its large interlayer can allow fast lithium diffusion in 3.0-1.0 V. However, the low theoretical capacity (167 mAh g-1 ) limits its wide application. Here, by fine tuning the lithiation depth of MoS2 , we demonstrate that its parent layered structure can be preserved with expanded interlayers while cycling in 3.0-0.6 V. The deeper lithiation and maintained crystalline structure endows commercially micrometer-sized MoS2 with a capacity of 232 mAh g-1 at 0.05 A g-1 and circa 92 % capacity retention after 1000 cycles at 1.0 A g-1 . Moreover, the enlarged interlayers enable MoS2 to release a capacity of 165 mAh g-1 at 5.0 A g-1 , which is double the capacity obtained under 3.0-1.0 V at the same rate. Our strategy of controlling the lithiation depth of MoS2 to avoid fracture ushers in new possibilities to enhance the lithium storage of layered transition-metal dichalcogenides.

Correlating the Surface Basicity of Metal Oxides with Photocatalytic Hydroxylation of Boronic Acids to Alcohols.

Photoredox catalysis provides opportunities in harnessing clean and green resources such as sunlight and O2 , while the acid and base surface sites of metal oxides are critical for industrial catalysis such as oil cracking. The contribution of metal oxide surfaces towards photocatalytic aerobic reactions was elucidated, as demonstrated through the hydroxylation of boronic acids to alcohols. The strength and proximity of the surface base sites appeared to be two key factors in driving the reaction; basic and amphoteric oxides such as MgO, TiO2 , ZnO, and Al2 O3 enabled high alcohol yields, while acidic oxides such as SiO2 and B2 O3 gave only low yields. The reaction is tunable to different irradiation sources by merely selecting photosensitizers of compatible excitation wavelengths. Such surface complexation mechanisms between reactants and earth abundant materials can be effectively utilized to achieve a wider range of photoredox reactions.

Al(2)O(3) Surface Complexation for Photocatalytic Organic Transformations.

The use of sunlight to drive organic reactions constitutes a green and sustainable strategy for organic synthesis. Herein, we discovered that the earth-abundant aluminum oxide (Al2O3) though paradigmatically known to be an insulator could induce an immense increase in the selective photo-oxidation of different benzyl alcohols in the presence of a large variety of dyes and O2. This unique phenomenon is based on the surface complexation of benzyl alcohol (BnOH) with the Brønsted base sites on Al2O3, which reduces its oxidation potential and causes an upshift in its HOMO for electron abstraction by the dye. The surface complexation of O2 with Al2O3 also activates the adsorbed O2 for receiving electrons from the photoexcited dyes. This discovery brings forth a new understanding on utilizing surface complexation mechanisms between the reactants and earth abundant materials to effectively achieve a wider range of photoredox reactions.

Colorimetric Detection of Creatinine Based on Plasmonic Nanoparticles via Synergistic Coordination Chemistry.

A simple and portable colorimetric assay for creatinine detection is fabricated based on the synergistic coordination of creatinine and uric acid with Hg(2+) on the surface of gold nanoparticles, which exhibits good selectivity and sensitivity. Point-of-care clinical creatinine monitoring can be supported for monitoring renal function and diagnosing corresponding renal diseases at home.

Optoelectronics of organic nanofibers formed by co-assembly of porphyrin and perylenediimide.

Organic nanofibers are formed by simple ionic co-assembly of positively charged porphyrin (electron donor) and negatively charged perylenediimide (electron acceptor) derivatives in aqueous solution. Two kinds of electron transfer routes between electron donor and electron acceptor under light excitation in nanofibers are confirmed by DFT calculations and experimental data.

Microstructured graphene arrays for highly sensitive flexible tactile sensors.

A highly sensitive tactile sensor is devised by applying microstructured graphene arrays as sensitive layers. The combination of graphene and anisotropic microstructures endows this sensor with an ultra-high sensitivity of -5.53 kPa(-1) , an ultra-fast response time of only 0.2 ms, as well as good reliability, rendering it promising for the application of tactile sensing in artificial skin and human-machine interface.

A synergistic capture strategy for enhanced detection and elimination of bacteria.

Despite the advanced detection and sterilization techniques available today, the sensitive diagnosis and complete elimination of bacterial infections remain a significant challenge. A strategy is reported for efficient bacterial capture (ca. 90%) based on the synergistic effect of the nanotopography and surface chemistry of the substrate on bacterial attachment and adhesion. The outstanding bacterial-capture capability of the functionalized nanostructured substrate enables rapid and highly sensitive bacterial detection down to trace concentrations of pathogenic bacteria (10 colony-forming units mL(-1)). In addition, this synergistic biocapture substrate can be used for efficient bacterial elimination and shows great potential for clinical antibacterial applications.

Unravelling the correlation between the aspect ratio of nanotubular structures and their electrochemical performance to achieve high-rate and long-life lithium-ion batteries.

The fundamental understanding of the relationship between the nanostructure of an electrode and its electrochemical performance is crucial for achieving high-performance lithium-ion batteries (LIBs). In this work, the relationship between the nanotubular aspect ratio and electrochemical performance of LIBs is elucidated for the first time. The stirring hydrothermal method was used to control the aspect ratio of viscous titanate nanotubes, which were used to fabricate additive-free TiO2 -based electrode materials. We found that the battery performance at high charging/discharging rates is dramatically boosted when the aspect ratio is increased, due to the optimization of electronic/ionic transport properties within the electrode materials. The proof-of-concept LIBs comprising nanotubes with an aspect ratio of 265 can retain more than 86 % of their initial capacity over 6000 cycles at a high rate of 30 C. Such devices with supercapacitor-like rate performance and battery-like capacity herald a new paradigm for energy storage systems.

Acidic media enables oxygen-tolerant electrosynthesis of multicarbon products from simulated flue gas.

Renewable electricity powered electrochemical CO2 reduction (CO2R) offers a valuable method to close the carbon cycle and reduce our overreliance on fossil fuels. However, high purity CO2 is usually required as feedstock, which potentially decreases the feasibility and economic viability of the process. Direct conversion of flue gas is an attractive option but is challenging due to the low CO2 concentration and the presence of O2 impurities. As a result, up to 99% of the applied current can be lost towards the undesired oxygen reduction reaction (ORR). Here, we show that acidic electrolyte can significantly suppress ORR on Cu, enabling generation of multicarbon products from simulated flue gas. Using a composite Cu and carbon supported single-atom Ni tandem electrocatalyst, we achieved a multicarbon Faradaic efficiency of 46.5% at 200 mA cm-2, which is ~20 times higher than bare Cu under alkaline conditions. We also demonstrate stable performance for 24 h with a multicarbon product full-cell energy efficiency of 14.6%. Strikingly, this result is comparable to previously reported acidic CO2R systems using pure CO2. Our findings demonstrate a potential pathway towards designing efficient electrolyzers for direct conversion of flue gas to value-added chemicals and fuels.

Nanocurvature-induced field effects enable control over the activity of single-atom electrocatalysts.

Tuning interfacial electric fields provides a powerful means to control electrocatalyst activity. Importantly, electric fields can modify adsorbate binding energies based on their polarizability and dipole moment, and hence operate independently of scaling relations that fundamentally limit performance. However, implementation of such a strategy remains challenging because typical methods modify the electric field non-uniformly and affects only a minority of active sites. Here we discover that uniformly tunable electric field modulation can be achieved using a model system of single-atom catalysts (SACs). These consist of M-N4 active sites hosted on a series of spherical carbon supports with varying degrees of nanocurvature. Using in-situ Raman spectroscopy with a Stark shift reporter, we demonstrate that a larger nanocurvature induces a stronger electric field. We show that this strategy is effective over a broad range of SAC systems and electrocatalytic reactions. For instance, Ni SACs with optimized nanocurvature achieved a high CO partial current density of ~400 mA cm-2 at >99% Faradaic efficiency for CO2 reduction in acidic media.

Electrified hydrocarbon-to-oxygenates coupled to hydrogen evolution for efficient greenhouse gas mitigation.

Chemicals manufacture is among the top greenhouse gas contributors. More than half of the associated emissions are attributable to the sum of ammonia plus oxygenates such as methanol, ethylene glycol and terephthalic acid. Here we explore the impact of electrolyzer systems that couple electrically-powered anodic hydrocarbon-to-oxygenate conversion with cathodic H2 evolution reaction from water. We find that, once anodic hydrocarbon-to-oxygenate conversion is developed with high selectivities, greenhouse gas emissions associated with fossil-based NH3 and oxygenates manufacture can be reduced by up to 88%. We report that low-carbon electricity is not mandatory to enable a net reduction in greenhouse gas emissions: global chemical industry emissions can be reduced by up to 39% even with electricity having the carbon footprint per MWh available in the United States or China today. We conclude with considerations and recommendations for researchers who wish to embark on this research direction.

Mechanically Durable Memristor Arrays Based on a Discrete Structure Design.

Memristors constitute a promising functional component for information storage and in-memory computing in flexible and stretchable electronics including wearable devices, prosthetics, and soft robotics. Despite tremendous efforts made to adapt conventional rigid memristors to flexible and stretchable scenarios, stretchable and mechanical-damage-endurable memristors, which are critical for maintaining reliable functions under unexpected mechanical attack, have never been achieved. Here, the development of stretchable memristors with mechanical damage endurance based on a discrete structure design is reported. The memristors possess large stretchability (40%) and excellent deformability (half-fold), and retain stable performances under dynamic stretching and releasing. It is shown that the memristors maintain reliable functions and preserve information after extreme mechanical damage, including puncture (up to 100 times) and serious tearing situations (fully diagonally cut). The structural strategy offers new opportunities for next-generation stretchable memristors with mechanical damage endurance, which is vital to achieve reliable functions for flexible and stretchable electronics even in extreme and highly dynamic environments.

A supertough electro-tendon based on spider silk composites.

Compared to transmission systems based on shafts and gears, tendon-driven systems offer a simpler and more dexterous way to transmit actuation force in robotic hands. However, current tendon fibers have low toughness and suffer from large friction, limiting the further development of tendon-driven robotic hands. Here, we report a super tough electro-tendon based on spider silk which has a toughness of 420 MJ/m3 and conductivity of 1,077 S/cm. The electro-tendon, mechanically toughened by single-wall carbon nanotubes (SWCNTs) and electrically enhanced by PEDOT:PSS, can withstand more than 40,000 bending-stretching cycles without changes in conductivity. Because the electro-tendon can simultaneously transmit signals and force from the sensing and actuating systems, we use it to replace the single functional tendon in humanoid robotic hand to perform grasping functions without additional wiring and circuit components. This material is expected to pave the way for the development of robots and various applications in advanced manufacturing and engineering.

Chloride-mediated selective electrosynthesis of ethylene and propylene oxides at high current density.

Chemicals manufacturing consumes large amounts of energy and is responsible for a substantial portion of global carbon emissions. Electrochemical systems that produce the desired compounds by using renewable electricity offer a route to lower carbon emissions in the chemicals sector. Ethylene oxide is among the world's most abundantly produced commodity chemicals because of its importance in the plastics industry, notably for manufacturing polyesters and polyethylene terephthalates. We applied an extended heterogeneous:homogeneous interface, using chloride as a redox mediator at the anode, to facilitate the selective partial oxidation of ethylene to ethylene oxide. We achieved current densities of 1 ampere per square centimeter, Faradaic efficiencies of ~70%, and product specificities of ~97%. When run at 300 milliamperes per square centimeter for 100 hours, the system maintained a 71(±1)% Faradaic efficiency throughout.

An Artificial Somatic Reflex Arc.

The emulation of human sensation, perception, and action processes has become a major challenge for bioinspired intelligent robotics, interactive human-machine interfacing, and advanced prosthetics. Reflex actions, enabled through reflex arcs, are important for human and higher animals to respond to stimuli from environment without the brain processing and survive the risks of nature. An artificial reflex arc system that emulates the functions of the reflex arc simplifies the complex circuit design needed for "central-control-only" processes and becomes a basic electronic component in an intelligent soft robotics system. An artificial somatic reflex arc that enables the actuation of electrochemical actuators in response to the stimulation of tactile pressures is reported. Only if the detected pressure by the pressure sensor is above the stimulus threshold, the metal-organic-framework-based threshold controlling unit (TCU) can be activated and triggers the electrochemical actuators to complete the motion. Such responding mechanism mimics the all-or-none law in the human nervous system. As a proof of concept, the artificial somatic reflex arc is successfully integrated into a robot to mimic the infant grasp reflex. This work provides a unique and simplifying strategy for developing intelligent soft robotics, next-generation human-machine interfaces, and neuroprosthetics.

Thermal-Disrupting Interface Mitigates Intercellular Cohesion Loss for Accurate Topical Antibacterial Therapy.

Bacterial infections remain a leading threat to global health because of the misuse of antibiotics and the rise in drug-resistant pathogens. Although several strategies such as photothermal therapy and magneto-thermal therapy can suppress bacterial infections, excessive heat often damages host cells and lengthens the healing time. Here, a localized thermal managing strategy, thermal-disrupting interface induced mitigation (TRIM), is reported, to minimize intercellular cohesion loss for accurate antibacterial therapy. The TRIM dressing film is composed of alternative microscale arrangement of heat-responsive hydrogel regions and mechanical support regions, which enables the surface microtopography to have a significant effect on disrupting bacterial colonization upon infrared irradiation. The regulation of the interfacial contact to the attached skin confines the produced heat and minimizes the risk of skin damage during thermoablation. Quantitative mechanobiology studies demonstrate the TRIM dressing film with a critical dimension for surface features plays a critical role in maintaining intercellular cohesion of the epidermis during photothermal therapy. Finally, endowing wound dressing with the TRIM effect via in vivo studies in S. aureus infected mice demonstrates a promising strategy for mitigating the side effects of photothermal therapy against a wide spectrum of bacterial infections, promoting future biointerface design for antibacterial therapy.

Tactile Chemomechanical Transduction Based on an Elastic Microstructured Array to Enhance the Sensitivity of Portable Biosensors.

Tactile sensors capable of perceiving biophysical signals such as force, pressure, or strain have attracted extensive interest for versatile applications in electronic skin, noninvasive healthcare, and biomimetic prostheses. Despite these great achievements, they are still incapable of detecting bio/chemical signals that provide even more meaningful and precise health information due to the lack of efficient transduction principles. Herein, a tactile chemomechanical transduction strategy that enables the tactile sensor to perceive bio/chemical signals is proposed. In this methodology, pyramidal tactile sensors are linked with biomarker-induced gas-producing reactions, which transduce biomarker signals to electrical signals in real time. The method is advantageous as it enhances electrical signals by more than tenfold based on a triple-step signal amplification strategy, as compared to traditional electrical biosensors. It also constitutes a portable and general platform capable of quantifying a wide spectrum of targets including carcinoembryonic antigen, interferon-γ, and adenosine. Such tactile chemomechanical transduction would greatly broaden the application of tactile sensors toward bio/chemical signals perception which can be used in ultrasensitive portable biosensors and chemical-responsive chemomechanical systems.