Substantial lifetime enhancement for Si-based photoanodes enabled by amorphous TiO2 coating with improved stoichiometry.

Amorphous titanium dioxide (TiO2) film coating by atomic layer deposition (ALD) is a promising strategy to extend the photoelectrode lifetime to meet the industrial standard for solar fuel generation. To realize this promise, the essential structure-property relationship that dictates the protection lifetime needs to be uncovered. In this work, we reveal that in addition to the imbedded crystalline phase, the presence of residual chlorine (Cl) ligands is detrimental to the silicon (Si) photoanode lifetime. We further demonstrate that post-ALD in-situ water treatment can effectively decouple the ALD reaction completeness from crystallization. The as-processed TiO2 film has a much lower residual Cl concentration and thus an improved film stoichiometry, while its uniform amorphous phase is well preserved. As a result, the protected Si photoanode exhibits a substantially improved lifetime to ~600 h at a photocurrent density of more than 30 mA/cm2. This study demonstrates a significant advancement toward sustainable hydrogen generation.

Nucleation Kinetics and Structure Evolution of Quasi-Two-Dimensional ZnO at the Air-Water Interface: An In Situ Time-Resolved Grazing Incidence X-ray Scattering Study.

The design and synthesis of high-quality two-dimensional (2D) materials with desired morphology are essential for property control. One critical challenge that impedes the understanding and control of 2D crystal nucleation and growth is the inability of direct observation of the nanocrystal evolution process with high enough time resolution. Here, we demonstrated an in situ X-ray scattering approach that directly reveals 2D wurtzite ZnO nanosheet growth at the air-water interface. The time-resolved grazing incidence X-ray diffraction (GID) and grazing incidence X-ray off-specular scattering (GIXOS) results uncovered a lateral to vertical growth kinetics switch phenomenon in the ZnO nanosheet growth. This switch represents the 2D to three-dimensional (3D) crystal structure evolution, which governs the size and thickness of nanosheets, respectively. This phenomenon can guide 2D nanocrystal synthesis with rationally controlled size and thickness. Our work opens a new pathway toward the understanding of 2D nanomaterial growth kinetics based on time-resolved liquid surface grazing incidence X-ray techniques.

Energy Harvesting Floor from Commercial Cellulosic Materials for a Self-Powered Wireless Transmission Sensor System.

Cellulose-based materials have gained increasing attention for the development of low-cost, eco-friendly technologies, and more recently, as functional materials in triboelectric nanogenerators (TENGs). However, the low output performance of cellulose-based TENGs severely restricts their versatility and employment in emerging smart building and smart city applications. Here, we report a high output performance of a commercial cellulosic material-based energy harvesting floor (CEHF). Benefiting from the significant difference in the triboelectric properties between weighing and nitrocellulose papers, high surface roughness achieved by a newly developed mechanical exfoliation method, and large overall contact area via a multilayered device structure, the CEHF (25 cm × 15 cm × 1.2 cm) exhibits excellent output performance with a maximum output voltage, current, and power peak values of 360 V, 250 µA, and 5 mW, respectively. It can be directly installed or integrated with regular flooring products to effectively convert human body movements into electricity and shows good durability and stability. Moreover, a wireless transmission sensing system that can produce a 1:1 footstep-to-signal (transmitted and received) ratio is instantaneously powered by a TENG based entirely on cellulosic materials for the first time. This work provides a feasible and effective way to utilize commercial cellulosic materials to construct self-powered wireless transmission systems for real-time sensing applications.

Prevention of Hepatic Ischemia-Reperfusion Injury by Carbohydrate-Derived Nanoantioxidants.

Hepatic ischemia-reperfusion injury (IRI), which mainly results from excessive reactive oxygen species (ROS) generated by a reperfusion burst of oxygen, has long been a major cause of liver dysfunction and failure after surgical procedures. Here, a monodispersed hydrophilic carbohydrate-derived nanoparticle (C-NP) was synthesized as a nanoantioxidant that could effectively prevent hepatic IRI. The spherical C-NPs had a size of ∼78 ± 11.3 nm covered with polar surface groups. They were well dispersible in water with good colloidal stability, nontoxicity, and good ROS scavenging capability. The C-NPs also exhibited good circulation lifetime, effective delivery to liver, and gradual degradability with an ability to assist the IRI group maintaining a normal and healthy liver status. The pathology mechanism of C-NPs in hepatic IRI was confirmed to be scavenging of excessive ROS by C-NPs. The effective therapeutic treatment of C-NPs in living animals revealed a great potential in clinical prevention for hepatic IRI.

In vitro study of enhanced photodynamic cancer cell killing effect by nanometer-thick gold nanosheets.

Photodynamic therapy (PDT) by near-infrared (NIR) irradiation is a promising technique for treating various cancers. Here, we reported the development of free-standing wafer-scale Au nanosheets (NSs) that exhibited an impressive PDT effect. The Au NSs were synthesized by ionic layer epitaxy at the air-water interface with a uniform thickness in the range from 2 to 8.5 nm. These Au NSs were found very effective in generating singlet oxygen under NIR irradiation. In vitro cellular study showed that the Au NSs had very low cytotoxicity and high PDT efficiency due to their uniform 2D morphology. Au NSs could kill cancer cells after 5 min NIR irradiation with little heat generation. This performance is comparable to using 10 times mass loading of Au nanoparticles (NPs). This work suggests that two-dimensional (2D) Au NSs could be a new type of biocompatible nanomaterial for PDT of cancer with an extraordinary photon conversion and cancer cell killing efficiency.

Enhanced Ferromagnetism from Organic-Cerium Oxide Hybrid Ultrathin Nanosheets.

Room-temperature ferromagnetism in two-dimensional (2D) oxide materials is an intriguing phenomenon for spintronic applications. Here, we report significantly enhanced room-temperature ferromagnetism observed from ultrathin cerium oxide nanosheets hybridized with organic surfactant molecules. The hybrid nanosheets were synthesized by ionic layer epitaxy over a large area at the water-air interface. The nanosheets exhibited a saturation magnetization of 0.149 emu/g as their thickness reduced to 0.67 nm. This value was 5 times higher than that for CeO2 thin films and more than 20 times higher than that for CeO2 nanoparticles. The magnetization was attributed to the high concentration (15.5%) of oxygen vacancies stabilized by surfactant hybridization as well as electron transfer between organic and oxide layers. This work brings an effective strategy of introducing strong ferromagnetism to functional oxide materials, which leads to a promising route toward exploring new physical properties in 2D hybrid nanomaterials.

Implanted Battery-Free Direct-Current Micro-Power Supply from in Vivo Breath Energy Harvesting.

In vivo biomechanical energy harvesting by implanted nanogenerators (i-NGs) is promising for self-powered implantable medical devices (IMDs). One critical challenge to reach practical applications is the requirement of continuous direct-current (dc) output, while the low-frequency body activities typically generate discrete electrical pulses. Here, we developed an ultrastretchable micrograting i-NG system that could function as a battery-free dc micro-power supply. Packaged by a soft silicone elastomer with a cavity design, the i-NG exhibited an ultralow Young's modulus of ∼45 kPa and a high biocompatibility to soft biological tissues. The i-NG was implanted inside the abdominal cavity of Sprague Dawley adult rats and directly converted the slow diaphragm movement during normal respiration into a high-frequency alternative current electrical output, which was readily transmitted into a continuous ∼2.2 V dc output after being integrated with a basic electrical circuit. A light-emitting diode was constantly operated by the breath-driven i-NG without the aid of any battery component. This solely biomechanical energy-driven dc micro-power supply offers a promising solution for the development of self-powered IMDs.

Simultaneous Enhancement of Charge Separation and Hole Transportation in a TiO2 -SrTiO3 Core-Shell Nanowire Photoelectrochemical System.

Efficient charge separation and transportation are key factors that determine the photoelectrochemical (PEC) water-splitting efficiency. Here, a simultaneous enhancement of charge separation and hole transportation on the basis of ferroelectric polarization in TiO2 -SrTiO3 core-shell nanowires (NWs) is reported. The SrTiO3 shell with controllable thicknesses generates a considerable spontaneous polarization, which effectively tunes the electrical band bending of TiO2 . Combined with its intrinsically high charge mobility, the ferroelectric SrTiO3 thin shell significantly improves the charge-separation efficiency (ηseparation ) with minimized influence on the hole-migration property of TiO2 photoelectrodes, leading to a drastically increased photocurrent density ( Jph ). Specifically, the 10 nm-thick SrTiO3 shell yields the highest Jph and ηseparation of 1.43 mA cm-2 and 87.7% at 1.23 V versus reversible hydrogen electrode, respectively, corresponding to 83% and 79% improvements compared with those of pristine TiO2 NWs. The PEC performance can be further manipulated by thermal treatment, and the control of SrTiO3 film thicknesses and electric poling directions. This work suggests a material with combined ferroelectric and semiconducting features could be a promising solution for advancing PEC systems by concurrently promoting the charge-separation and hole-transportation properties.