Construction of Nanoflower Cobalt-Based Catalyst for Methane-Free CO Hydrogenation to Hydrocarbon Reaction.

Methane and its oxidation product (i. e., CO2) are both greenhouse gases. In the product chain of CO hydrogenation to hydrocarbon reaction, methane is also an unwanted product due to its poor added value. Herein we investigated the effect of structure-directing agent urotropine on cobalt-based catalyst supported on Al-O-Zn type carrier and achieved an initial and pioneering exploration of methane-free CO hydrogenation to hydrocarbon reaction at mild CO conversion range. The catalyst modified by urotropine has a nanoflower micromorphology and can significantly change the reaction performance, almost completely eliminating the ability of the catalyst to inhibit C-C coupling within a mild CO conversion range, that is, it can produce no or less C1-C4 gaseous hydrocarbons, while rich in condensed hydrocarbons (i. e., C5+ hydrocarbon selectivity can reach as high as 92.8 %-100.0 %).

Redox-Enhanced Photoelectrochemical Activity in PHV/CdS Hybrid Film.

Semiconductive photocatalytic materials have received increasing attention recently due to their ability to transform solar energy into chemical fuels and photodegrade a wide range of pollutants. Among them, cadmium sulfide (CdS) nanoparticles have been extensively studied as semiconductive photocatalysts in previous studies on hydrogen generation and environmental purification due to their suitable bandgap and sensitive light response. However, the practical applications of CdS are limited by its low charge separation, which is caused by its weak ability to separate photo-generated electron-hole pairs. In order to enhance the photoelectrochemical activity of CdS, a polymer based on viologen (PHV) was utilized to create a series of PHV/CdS hybrid films so that the viologen unit could work as the electron acceptor to increase the charge separation. In this work, various electrochemical, spectroscopic, and microscopic methods were utilized to analyze the hybrid films, and the results indicated that introducing PHV can significantly improve the performance of CdS. The photoelectrochemical activities of the hybrid films were also evaluated at various ratios, and it was discovered that a PHV-to-CdS ratio of 2:1 was the ideal ratio for the hybrid films. In comparison with CdS nanoparticles, the PHV/CdS hybrid film has a relatively lower band gap, and it can inhibit the recombination of electrons and holes, enhancing its photoelectrochemical activities. All of these merits make the PHV/CdS hybrid film as a strong candidate for photocatalysis applications in the future.

In Situ Visualization of Dynamic Cellular Effects of Phospholipid Nanoparticles via High-Speed Scanning Ion Conductance Microscopy.

Phospholipid nanoparticles have been actively employed for numerous biomedical applications. A key factor in ensuring effective and safe applications of these nanomaterials is the regulation of their interactions with target cells, which is significantly dependent on an in-depth understanding of the nanoparticle-cell interactions. To date, most studies investigating these nano-bio interactions have been performed under static conditions and may lack crucial real-time information. It is, however, noteworthy that the nanoparticle-cell interactions are highly dynamic. Consequently, to gain a deeper insight into the cellular effects of phospholipid nanoparticles, real-time observation of cellular dynamics after nanoparticle introduction is necessary. Herein, a proof-of-concept in situ visualization of the dynamic cellular effects of sub-100 nm phospholipid nanoparticles using high-speed scanning ion conductance microscopy (HS-SICM) is reported. It is revealed that upon introduction into the cellular environment, within a short timescale of hundreds of seconds, phospholipid nanoparticles can selectively modulate the edge motility and surface roughness of healthy fibroblast and cancerous epithelial cells. Furthermore, the dynamic deformation profiles of these cells can be selectively altered in the presence of phospholipid nanoparticles. This work is anticipated to further shed light on the real-time nanoparticle-cell interactions for improved formulation of phospholipid nanoparticles for numerous bioapplications.

Reductive Carbon-Carbon Coupling on Metal Sites Regulates Photocatalytic CO2 Reduction in Water Using ZnSe Quantum Dots.

Colloidal quantum dots (QDs) consisting of precious-metal-free elements show attractive potentials towards solar-driven CO2 reduction. However, the inhibition of hydrogen (H2 ) production in aqueous solution remains a challenge. Here, we describe the first example of a carbon-carbon (C-C) coupling reaction to block the competing H2 evolution in photocatalytic CO2 reduction in water. In a specific system taking ZnSe QDs as photocatalysts, the introduction of furfural can significantly suppress H2 evolution leading to CO evolution with a rate of ≈5.3 mmol g-1 h-1 and a turnover number (TON) of >7500 under 24 h visible light. Meanwhile, furfural is upgraded to the self-coupling product with a yield of 99.8 % based on the consumption of furfural. Mechanistic insights show that the reductive furfural coupling reaction occurs on surface Zn-sites to consume electrons and protons originally used for H2 production, while the CO formation pathway at surface anion vacancies from CO2 remains.

Rational Design of Dot-on-Rod Nano-Heterostructure for Photocatalytic CO2 Reduction: Pivotal Role of Hole Transfer and Utilization.

Inspired by green plants, artificial photosynthesis has become one of the most attractive approaches toward carbon dioxide (CO2 ) valorization. Semiconductor quantum dots (QDs) or dot-in-rod (DIR) nano-heterostructures have gained substantial research interest in multielectron photoredox reactions. However, fast electron-hole recombination or sluggish hole transfer and utilization remains unsatisfactory for their potential applications. Here, the first application of a well-designed ZnSe/CdS dot-on-rods (DORs) nano-heterostructure for efficient and selective CO2 photoreduction with H2 O as an electron donor is presented. In-depth spectroscopic studies reveal that surface-anchored ZnSe QDs not only assist ultrafast (≈2 ps) electron and hole separation, but also promote interfacial hole transfer participating in oxidative half-reactions. Surface photovoltage (SPV) spectroscopy provides a direct image of spatially separated electrons in CdS and holes in ZnSe. Therefore, ZnSe/CdS DORs photocatalyze CO2 to CO with a rate of ≈11.3 µmol g-1 h-1 and ≥85% selectivity, much higher than that of ZnSe/CdS DIRs or pristine CdS nanorods under identical conditions. Obviously, favored energy-level alignment and unique morphology balance the utilization of electrons and holes in this nano-heterostructure, thus enhancing the performance of artificial photosynthetic solar-to-chemical conversion.

A wireless and battery-free wound infection sensor based on DNA hydrogel.

The confluence of wireless technology and biosensors offers the possibility to detect and manage medical conditions outside of clinical settings. Wound infections represent a major clinical challenge in which timely detection is critical for effective interventions, but this is currently hindered by the lack of a monitoring technology that can interface with wounds, detect pathogenic bacteria, and wirelessly transmit data. Here, we report a flexible, wireless, and battery-free sensor that provides smartphone-based detection of wound infection using a bacteria-responsive DNA hydrogel. The engineered DNA hydrogels respond selectively to deoxyribonucleases associated with pathogenic bacteria through tunable dielectric changes, which can be wirelessly detected using near-field communication. In a mouse acute wound model, we demonstrate that the wireless sensor can detect physiologically relevant amounts of Staphylococcus aureus even before visible manifestation of infection. These results demonstrate strategies for continuous infection monitoring, which may facilitate improved management of surgical or chronic wounds.

A flexible multiplexed immunosensor for point-of-care in situ wound monitoring.

Chronic wounds arise from interruption of normal healing due to many potential pathophysiological factors. Monitoring these multivariate factors can provide personalized diagnostic information for wound management, but current sensing technologies use complex laboratory tests or track a limited number of wound parameters. We report a flexible biosensing platform for multiplexed profiling of the wound microenvironment, inflammation, and infection state at the point of care. This platform integrates a sensor array for measuring inflammatory mediators [tumor necrosis factor-α, interleukin-6 (IL-6), IL-8, and transforming growth factor-ß1], microbial burden (Staphylococcus aureus), and physicochemical parameters (temperature and pH) with a microfluidic wound exudate collector and flexible electronics for wireless, smartphone-based data readout. We demonstrate in situ multiplexed monitoring in a mouse wound model and also profile wound exudates from patients with venous leg ulcers. This technology may facilitate more timely and personalized wound management to improve chronic wound healing outcomes.

Simultaneous Conduction and Valence Band Regulation of Indium-Based Quantum Dots for Efficient H2 Photogeneration.

Indium-based chalcogenide semiconductors have been served as the promising candidates for solar H2 evolution reaction, however, the related studies are still in its infancy and the enhancement of efficiency remains a grand challenge. Here, we report that the photocatalytic H2 evolution activity of quantized indium chalcogenide semiconductors could be dramatically aroused by the co-decoration of transition metal Zn and Cu. Different from the traditional metal ion doping strategies which only focus on narrowing bandgap for robust visible light harvesting, the conduction and valence band are coordinately regulated to realize the bandgap narrowing and the raising of thermodynamic driving force for proton reduction, simultaneously. Therefore, the as-prepared noble metal-free Cu0.4-ZnIn2S4 quantum dots (QDs) exhibits extraordinary activity for photocatalytic H2 evolution. Under optimal conditions, the Cu0.4-ZnIn2S4 QDs could produce H2 with the rate of 144.4 µmol h-1 mg-1, 480-fold and 6-fold higher than that of pristine In2S3 QDs and Cu-doped In2S3 QDs counterparts respectively, which is even comparable with the state-of-the-art cadmium chalcogenides QDs.

Flexible Hybrid Sensors for Health Monitoring: Materials and Mechanisms to Render Wearability.

Wearable electronics have revolutionized the way physiological parameters are sensed, detected, and monitored. In recent years, advances in flexible and stretchable hybrid electronics have created emergent properties that enhance the compliance of devices to our skin. With their unobtrusive attributes, skin conformable sensors enable applications toward real-time disease diagnosis and continuous healthcare monitoring. Herein, critical perspectives of flexible hybrid electronics toward the future of digital health monitoring are provided, emphasizing its role in physiological sensing. In particular, the strategies within the sensor composition to render flexibility and stretchability while maintaining excellent sensing performance are considered. Next, novel approaches to the functionalization of the sensor for physical or biochemical stimuli are extensively covered. Subsequently, wearable sensors measuring physical parameters such as strain, pressure, temperature, as well as biological changes in metabolites and electrolytes are reported. Finally, their implications toward early disease detection and monitoring are discussed, concluding with a future perspective into the challenges and opportunities in emerging wearable sensor designs for the next few years.

Susceptible Surface Sulfide Regulates Catalytic Activity of CdSe Quantum Dots for Hydrogen Photogeneration.

Semiconducting quantum dots (QDs) have recently triggered a huge interest in constructing efficient hydrogen production systems. It is well established that a large fraction of surface atoms of QDs need ligands to stabilize and avoid them from aggregating. However, the influence of the surface property of QDs on photocatalysis is rather elusive. Here, the surface regulation of CdSe QDs is investigated by surface sulfide ions (S2- ) for photocatalytic hydrogen evolution. Structural and spectroscopic study shows that with gradual addition of S2- , S2- first grows into the lattice and later works as ligands on the surface of CdSe QDs. In-depth transient spectroscopy reveals that the initial lattice S2- accelerates electron transfer from QDs to cocatalyst, and the following ligand S2- mainly facilitates hole transfer from QDs to the sacrificial agent. As a result, a turnover frequency (TOF) of 7950 h-1 can be achieved by the S2- modified CdSe QDs, fourfold higher than that of original mercaptopropionic acid (MPA) capped CdSe QDs. Clearly, the simple surface S2- modification of QDs greatly increases the photocatalytic efficiency, which provides subtle methods to design new QD material for advanced photocatalysis.

Self-assembled inorganic clusters of semiconducting quantum dots for effective solar hydrogen evolution.

Owing to promoted electron-hole separation, the catalytic activity of semiconducting quantum dots (QDs) towards solar hydrogen (H2) production has been significantly enhanced by forming self-assembled clusters with ZnSe QDs made ex situ. Taking advantage of the favored interparticle hole transfer to ZnSe QDs, the rate of solar H2 evolution of CdSe QDs can be increased to ∼30 000 µmol h-1 g-1 with ascorbic acid as the sacrificial reagent, ∼150-fold higher than that of bare CdSe QDs clusters under the same conditions.

Nonstoichiometric Cux Iny S Quantum Dots for Efficient Photocatalytic Hydrogen Evolution.

Unlike their bulk counterpart, Cux Iny S quantum dots (QDs) prepared by an aqueous synthetic approach, show promising activity for photocatalytic hydrogen evolution, which is competitive with the state-of-the-art Cd chalcogen QDs. Moreover, the as-prepared Cux Iny S QDs with In-rich composition show much better efficiency than the stoichiometric ones (Cu/In=1:1).

Wearable Microfluidic Diaphragm Pressure Sensor for Health and Tactile Touch Monitoring.

Flexible pressure sensors have many potential applications in wearable electronics, robotics, health monitoring, and more. In particular, liquid-metal-based sensors are especially promising as they can undergo strains of over 200% without failure. However, current liquid-metal-based strain sensors are incapable of resolving small pressure changes in the few kPa range, making them unsuitable for applications such as heart-rate monitoring, which require a much lower pressure detection resolution. In this paper, a microfluidic tactile diaphragm pressure sensor based on embedded Galinstan microchannels (70 µm width × 70 µm height) capable of resolving sub-50 Pa changes in pressure with sub-100 Pa detection limits and a response time of 90 ms is demonstrated. An embedded equivalent Wheatstone bridge circuit makes the most of tangential and radial strain fields, leading to high sensitivities of a 0.0835 kPa-1 change in output voltage. The Wheatstone bridge also provides temperature self-compensation, allowing for operation in the range of 20-50 °C. As examples of potential applications, a polydimethylsiloxane (PDMS) wristband with an embedded microfluidic diaphragm pressure sensor capable of real-time pulse monitoring and a PDMS glove with multiple embedded sensors to provide comprehensive tactile feedback of a human hand when touching or holding objects are demonstrated.

3D Printed "Earable" Smart Devices for Real-Time Detection of Core Body Temperature.

Real-time detection of basic physiological parameters such as blood pressure and heart rate is an important target in wearable smart devices for healthcare. Among these, the core body temperature is one of the most important basic medical indicators of fever, insomnia, fatigue, metabolic functionality, and depression. However, traditional wearable temperature sensors are based upon the measurement of skin temperature, which can vary dramatically from the true core body temperature. Here, we demonstrate a three-dimensional (3D) printed wearable "earable" smart device that is designed to be worn on the ear to track core body temperature from the tympanic membrane (i.e., ear drum) based on an infrared sensor. The device is fully integrated with data processing circuits and a wireless module for standalone functionality. Using this smart earable device, we demonstrate that the core body temperature can be accurately monitored regardless of the environment and activity of the user. In addition, a microphone and actuator are also integrated so that the device can also function as a bone conduction hearing aid. Using 3D printing as the fabrication method enables the device to be customized for the wearer for more personalized healthcare. This smart device provides an important advance in realizing personalized health care by enabling real-time monitoring of one of the most important medical parameters, core body temperature, employed in preliminary medical screening tests.

Assembling metallic 1T-MoS2 nanosheets with inorganic-ligand stabilized quantum dots for exceptional solar hydrogen evolution.

Due to their enhanced light harvesting, favored interfacial charge transfer and excellent proton reduction activity, hybrid photocatalysts of metallic 1T-MoS2 nanosheets and inorganic-ligand stabilized CdSe/ZnS QDs obtained via a self-assembly approach can produce H2 gas with a rate of ∼155 ± 3.5 µmol h-1 mg-1 under visible-light irradiation (λ = 410 nm), the most exceptional performance of solar H2 evolution using MoS2 as a cocatalyst known to date.

Self-Assembled Framework Enhances Electronic Communication of Ultrasmall-Sized Nanoparticles for Exceptional Solar Hydrogen Evolution.

Colloidal quantum dots (QDs) have demonstrated great promise in artificial photosynthesis. However, the ultrasmall size hinders its controllable and effective interaction with cocatalysts. To improve the poor interparticle electronic communication between free QD and cocatalyst, we design here a self-assembled architecture of nanoparticles, QDs and Pt nanoparticles, simply jointed together by molecular polyacrylate to greatly enhance the rate and efficiency of interfacial electron transfer (ET). The enhanced interparticle electronic communication is confirmed by femtosecond transient absorption spectroscopy and X-ray transient absorption. Taking advantage of the enhanced interparticle ET with a time scale of ∼65 ps, 5.0 mL of assembled CdSe/CdS QDs/cocatalysts solution produces 94 ± 1.5 mL (4183 ± 67 µmol) of molecular H2 in 8 h, giving rise to an internal quantum yield of ∼65% in the first 30 min and a total turnover number of >1.64â€¯× 107 per Pt nanoparticle. This study demonstrates that self-assembly is a promising way to improve the sluggish kinetics of the interparticle ET process, which is the key step for advanced H2 photosynthesis.

Tracking Co(I) Intermediate in Operando in Photocatalytic Hydrogen Evolution by X-ray Transient Absorption Spectroscopy and DFT Calculation.

X-ray transient absorption spectroscopy (XTA) and optical transient spectroscopy (OTA) were used to probe the Co(I) intermediate generated in situ from an aqueous photocatalytic hydrogen evolution system, with [RuII(bpy)3]Cl2·6H2O as the photosensitizer, ascorbic acid/ascorbate as the electron donor, and the Co-polypyridyl complex ([CoII(DPA-Bpy)Cl]Cl) as the precatalyst. Upon exposure to light, the XTA measured at Co K-edge visualizes the grow and decay of the Co(I) intermediate, and reveals its Co-N bond contraction of 0.09 ± 0.03 Å. Density functional theory (DFT) calculations support the bond contraction and illustrate that the metal-to-ligand π back-bonding greatly stabilizes the penta-coordinated Co(I) intermediate, which provides easy photon access. To the best of our knowledge, this is the first example of capturing the penta-coordinated Co(I) intermediate in operando with bond contraction by XTA, thereby providing new insights for fundamental understanding of structure-function relationship of cobalt-based molecular catalysts.

Hole-Accepting-Ligand-Modified CdSe QDs for Dramatic Enhancement of Photocatalytic and Photoelectrochemical Hydrogen Evolution by Solar Energy.

Solar H2 evolution of CdSe QDs can be significantly enhanced simply by introducing a suitable hole-accepting-ligand for achieving efficient hole extraction and transfer at the nanoscale interfaces, which opens an effective pathway for dissociation of excitons to generate long-lived charge separation, thus improving the solar-to-fuel conversion efficiency.

Visible light catalysis-assisted assembly of Ni(h)-QD hollow nanospheres in situ via hydrogen bubbles.

Hollow spheres are one of the most promising micro-/nanostructures because of their unique performance in diverse applications. Templates, surfactants, and structure-directing agents are often used to control the sizes and morphologies of hollow spheres. In this Article, we describe a simple method based on visible light catalysis for preparing hollow nanospheres from CdE (E = Te, Se, and S) quantum dots (QDs) and nickel (Ni(2+)) salts in aqueous media. In contrast to the well-developed traditional approaches, the hollow nanospheres of QDs are formed in situ by the photogeneration of hydrogen (H2) gas bubbles at room temperature. Each component, that is, the QDs, metal ions, ascorbic acid (H2A), and visible light, is essential for the formation of hollow nanospheres. The quality of the hollow nanospheres depends on the pH, metal ions, and wavelength and intensity of visible light used. Of the various metal ions investigated, including Cu(+), Cu(2+), Fe(2+), Fe(3+), Ni(2+), Mn(2+), RuCl5(2-), Ag(+), and PtCl4(2-), Ni(2+) ions showed the best ability to generate H2 and hollow-structured nanospheres under visible light irradiation. The average diameter and shell thickness of the nanospheres ranged from 10 to 20 nm and from 3 to 6 nm, respectively, which are values rarely reported in the literature. Studies using high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), inductively coupled plasma-mass spectroscopy (ICP-AES), and steady-state and time-resolved spectroscopy revealed the chemical nature of the hollow nanospheres. Additionally, the hollow-structured nanospheres exhibit excellent photocatalytic activity and stability for the generation of H2 with a rate constant of 21 µmol h(-1) mg(-1) and a turnover number (TON) of 137,500 or 30,250 for CdTe QDs or nickel, respectively, under visible light irradiation for 42 h.

Mechanistic insights into the interface-directed transformation of thiols into disulfides and molecular hydrogen by visible-light irradiation of quantum dots.

Quantum dots (QDs) offer new and versatile ways to harvest light energy. However, there are few examples involving the utilization of QDs in organic synthesis. Visible-light irradiation of CdSe QDs was found to result in virtually quantitative coupling of a variety of thiols to give disulfides and H2 without the need for sacrificial reagents or external oxidants. The addition of small amounts of nickel(II) salts dramatically improved the efficiency and conversion through facilitating the formation of hydrogen atoms, thereby leading to faster regeneration of the ground-state QDs. Mechanistic studies reveal that the coupling reaction occurs on the QD surfaces rather than in solution and offer a blueprint for how these QDs may be used in other photocatalytic applications. Because no sacrificial agent or oxidant is necessary and the catalyst is reusable, this method may be useful for the formation of disulfide bonds in proteins as well as in other systems sensitive to the presence of oxidants.