Hydrogen induced interface engineering in Fe2O3-TiO2 heterostructures for efficient charge separation for solar-driven water oxidation in photoelectrochemical cells.

Semiconductor heterostructure junctions are known to improve the water oxidation performance in photoelectrochemical (PEC) cells. Depending on the semiconductor materials involved, different kinds of junctions can appear, for instance, type II band alignment where the conduction and valence bands of the semiconductor materials are staggered with respect to each other. This band alignment allows for a charge separation of the photogenerated electron-hole pairs, where the holes will go from low-to-high valance band levels and vice versa for the electrons. For this reason, interface engineering has attracted intensive attention in recent years. In this work, a simplified model of the Fe2O3-TiO2 heterostructure was investigated via first-principles calculations. The results show that Fe2O3-TiO2 produces a type I band alignment in the heterojunction, which is detrimental to the water oxidation reaction. However, the results also show that interstitial hydrogens are energetically allowed in TiO2 and that they introduce states above the valance band, which can assist in the transfer of holes through the TiO2 layer. In response, well-defined planar Fe2O3-TiO2 heterostructures were manufactured, and measurements confirm the formation of a type I band alignment in the case of Fe2O3-TiO2, with very low photocurrent density as a result. However, once TiO2 was subjected to hydrogen treatment, there was a nine times higher photocurrent density at 1.50 V vs. the reversible hydrogen electrode under 1 sun illumination as compared to the original heterostructured photoanode. Via optical absorption, XPS analysis, and (photo)electrochemical measurements, it is clear that hydrogen treated TiO2 results in a type II band alignment in the Fe2O3-H:TiO2 heterostructure. This work is an example of how hydrogen doping in TiO2 can tailor the band alignment in TiO2-Fe2O3 heterostructures. As such, it provides valuable insights for the further development of similar material combinations.

Transoral Robotic Surgical Proficiency Via Real-Time Tactile Collision Awareness System.

OBJECTIVES: In 2009, the Food and Drug Administration approved the use of the surgical robotic system for removal of benign and malignant conditions of the upper aerodigestive tract. This novel application of robotic-assisted surgery, termed transoral robotic surgery (TORS), places robotic instruments and camera system through the mouth to reach recessed areas of the pharynx and larynx. Over the successive decade, there was a rapid adoption of TORS with a surgical growth rate that continues to increase. Despite the rapid clinical acceptance, the field of TORS has not yet seen substantive changes or advances in the technical shortcomings, the lack of which has restricted objective TORS-specific surgical skills assessment as well as subsequent skills improvement efforts. One of the primary technical challenges of TORS is operating in a confined space, where the robotic system is maneuvered within the restrictive boundaries of the mouth and throat. Due to these confined boundaries of the pharynx, instruments can frequently collide with anatomic structures such as teeth and bone, producing anatomic collisions. Therefore, we hypothesized that anatomic collisions negatively impact TORS surgical performance. Secondarily, we hypothesized that avoidance of unwanted anatomic collisions could improve TORS surgical proficiency. METHODS: Design and fidelity testing for a custom TORS training platform with an integrated anatomic collision-sensing system providing real-time tactile feedback is described. Following successful platform assembly and testing, validation study using the platform was carried through prospective surgical training with trial randomization. Twenty otolaryngology-head and neck surgery residents, each trainee performing three discrete mock surgical trials (n = 60), performed the initial system validation. Ten of the 20 residents were randomized to perform the surgical trials utilizing the real-time feedback system. The remaining 10 residents were randomized to perform the surgical trials without the feedback system, although the system still could record collision data. Surgical proficiency was measured by Global Evaluative Assessment of Robotic Skills (GEARS) score, time to completion, and tumor resection scores (categorical scale ranging 0-3, describing the adequacy of resection). RESULTS: Major anatomic collisions (greater than 5N of force) negatively affected GEARS robotic skills. A mixed model analysis demonstrated that for every additional occurrence of a major collision, GEARS robotic skills assessment score would decrease by 0.29 points (P = .04). Real-time collision awareness created significantly fewer major (> 5 N) anatomic collisions with the tactile feedback system active (n = 30, mean collisions = 2.9 ± 4.2) as compared with trials without tactile feedback (n = 30, mean collisions = 12.53 ± 23.23) (P < .001). The second assessment measure of time to completion was unaffected by the presence of collisions or by the use of tactile feedback system. The third proficiency assessment was measured with tumor resection grading. Tumor resection scores was significantly (P = .02) improved with collision awareness system activated than trials without collision awareness. CONCLUSION: In order to test our primary hypothesis, a novel TORS training platform was successfully developed that provides collision force measurements including frequency, severity, and duration of anatomic collisions. Additionally, the platform was modulated to provide real-time tactile feedback of the occurrence of out-of-field collisions. Utilizing this custom platform, our hypothesis that anatomic collisions during TORS diminishes surgical performance was supported. Additionally, our secondary hypothesis that subsequent reduction of anatomic collisions improves TORS proficiency was supported by the surgical trial. Dedicated investigation to characterize the effect size and clinical impact is required in order to translate this finding into training curriculums and into clinical utilization. LEVEL OF EVIDENCE: II (Randomized trial) Laryngoscope, 130:S1-S17, 2020.

Synergies of co-doping in ultra-thin hematite photoanodes for solar water oxidation: In and Ti as representative case.

Solar energy induced water splitting in photoelectrochemical (PEC) cells is one of the most sustainable ways of hydrogen production. The challenge is to develop corrosion resistant and chemically stable semiconductors that absorb sunlight in the visible region and, at the same time, have the band edges matching with the redox level of water. In this work, hematite (α-Fe2O3) thin films were prepared onto an indium-doped tin oxide (ITO; In:SnO2) substrate by e-beam evaporation of Fe, followed by air annealing at two different temperatures: 350 and 500 °C. The samples annealed at 500 °C show an in situ diffusion of indium from the ITO substrate to the surface of α-Fe2O3, where it acts as a dopant and enhances the photoelectrochemical properties of hematite. Structural, optical, chemical and photoelectrochemical analysis reveal that the diffusion of In at 500 °C enhances the optical absorption, increases the electrode-electrolyte contact area by changing the surface topology, improves the carrier concentration and shifts the flat band potential in the cathodic direction. Further enhancement in photocurrent density was observed by ex situ diffusion of Ti, deposited in the form of nanodisks, from the top surface to the bulk. The in situ In diffused α-Fe2O3 photoanode exhibits an improved photoelectrochemical performance, with a photocurrent density of 145 µA cm-2 at 1.23 VRHE, compared to 37 µA cm-2 for the photoanode prepared at 350 °C; it also decreases the photocurrent onset potential from 1.13 V to 1.09 V. However, the In/Ti co-doped sample exhibits an even higher photocurrent density of 290 µA cm-2 at 1.23 VRHE and the photocurrent onset potential decreases to 0.93 VRHE, which is attributed to the additional doping and to the surface becoming more favorable to charge separation.

Development of a Transoral Robotic Surgery Training Platform.

Transoral robotic surgery (TORS) presents unique challenges due to difficulty manipulating surgical instruments within the tight confines of the oral cavity. Collisions between the end effectors and anatomical structures can be visualized through the endoscope; however, instrument shaft collisions are outside of the field-of-view. Acquiring the requisite skill set to minimize these collisions is challenging due to the lack of an appropriate training platform. In this paper, we present a TORS training platform with an integrated collision sensing system and real-time haptic feedback. Preliminary testing involved the recruitment of 10 Otolaryngology residents assigned to `feedback' (N=5) and `no feedback' (N=5) groups. Each trainee performed three mock surgical procedures involving the resection of a tumor from the base of the tongue. Superior surgical performance was observed in the feedback group suggesting that haptic feedback will enhance the acquisition of surgical skills.

In†Situ Solid-State Synthesis of a AgNi/g-C3 N4 Nanocomposite for Enhanced Photoelectrochemical and Photocatalytic Activity.

A graphitic carbon nitride (g-C3 N4 ) polymer matrix was embedded with AgNi alloy nanoparticles using a simple and direct in situ solid-state heat treatment method to develop a novel AgNi/g-C3 N4 photocatalyst. The characterization confirms that the AgNi alloy particles are homogeneously distributed throughout the g-C3 N4 matrix. The catalyst shows excellent photoelectrochemical activity for water splitting with a maximum photocurrent density of 1.2 mA cm-2 , which is the highest reported for doped g-C3 N4 . Furthermore, a detailed experimental study of the photocatalytic degradation of Rhodamine B (RhB) dye using doped g-C3 N4 showed the highest reported degradation efficiency of approximately 95 % after 90 min. The electronic conductivity increased upon incorporation of AgNi alloy nanoparticles on g-C3 N4 and the material showed efficient charge carrier separation and transfer characteristics, which are responsible for the enhanced photoelectrochemical and photocatalytic performance under visible light.

Visible-Light-Driven Photoelectrochemical and Photocatalytic Performance of NaNbO3 /Ag2 S Core-Shell Heterostructures.

Herein, we report the fabrication of visible-light-active NaNbO3 /Ag2 S staggered-gap core-shell semiconductor heterostructures with excellent photoelectrochemical activity toward water splitting, and the degradation of a model pollutant (methylene blue) was also monitored. The heterostructures show a pronounced photocurrent density of approximately 2.44 mA cm(-2) at 0.9 V versus Ag/AgCl in 0.5 m Na2 SO4 and exhibit a positive shift in onset potential by approximately 1.1 V. The high photoactivity is attributed to the efficient photoinduced interfacial charge transfer (IFCT). The core-shell design alleviates the challenges associated with the electron-hole paths across semiconductor junctions and at the electrolyte-semiconductor interface. These properties demonstrate that NaNbO3 /Ag2 S core-shell heterostructures show promising visible-light photoactivity and are also efficient, stable, and recyclable photocatalysts.