Catalyst Regeneration via Chemical Oxidation Enables Long-Term Electrochemical Carbon Dioxide Reduction.

Electrochemical CO2 reduction (ECR) with industrially relevant current densities, high product selectivity, and long-term stability has been a long-sought goal. Unfortunately, copper (Cu) catalysts for producing valuable multicarbon (C2+) products undergo structural and morphological changes under ECR conditions, especially at high current densities, resulting in a rapid decrease in product selectivity. Herein, we report a catalyst regeneration strategy, one that employs an electrolysis method comprising alternating "on" and "off" operating regimes, to increase the operating stability of a Cu catalyst. We find that it increases operating lifetime many times, maintaining ethylene selectivity ≥40% for at least 200 h of electrolysis in neutral pH media at a current density of 150 mA cm-2 using a flow cell. We also demonstrate ECR to ethylene at a current density of 1 A cm-2 with ethylene selectivity ≥40% using a three-dimensional Cu gas diffusion electrode, finding that this system under these conditions is rendered stable for greater than 36 h. This work illustrates that Cu-based catalysts, once they have entered into the state conventionally considered to possess degraded catalytic activity, may be recovered to deliver high C2+ selectivity. We present evidence that the combination of short periods of electrolysis, which minimizes the morphological changes during "on" segments, with the progressive chemical oxidation of Cu atoms on the catalyst surface during "off" segments, united with the added effects of washing the accumulated salt and decreasing the catholyte temperature prolong together the catalyst's operating lifetime.

Impact of a prestrained graded InGaN/GaN interlayer towards enhanced optical characteristics of a multi-quantum well LED based on silicon substrate.

This paper presents alternate pairs of InGaN/GaN prestrained layers with varying indium compositions, which are inserted between the GaN/InGaN MQW active region and the n-GaN layer in a light-emitting diode (LED) nanostructure in order to obtain enhanced optical characteristics. The device is mounted on a silicon substrate followed by a GaN buffer layer that promotes charge injection by minimizing the energy barrier between the electrode and active layers. The designed device attains more than 2.897% enhancement in efficiency when compared with the conventional LED, which is attributed to the reduction of a polarization field within the MQW region. The proposed device with 15% indium composition in the prestrained layer attains a maximum efficiency of 85.21% and a minimized efficiency droop of 3.848% at an injection current of 40 mA, with high luminous power in the output spectral range. The device also shows a minimum blueshift in the spectral range, indicating a decrease in the piezoelectric polarization.

Full-Color Single Nanowire Pixels for Projection Displays.

Multicolor single InGaN/GaN dot-in-nanowire light emitting diodes (LEDs) were fabricated on the same substrate using selective area epitaxy. It is observed that the structural and optical properties of InGaN/GaN quantum dots depend critically on nanowire diameters. Photoluminescence emission of single InGaN/GaN dot-in-nanowire structures exhibits a consistent blueshift with increasing nanowire diameter. This is explained by the significantly enhanced indium (In) incorporation for nanowires with small diameters, due to the more dominant contribution for In incorporation from the lateral diffusion of In adatoms. Single InGaN/GaN nanowire LEDs with emission wavelengths across nearly the entire visible spectral were demonstrated on a single chip by varying the nanowire diameters. Such nanowire LEDs also exhibit superior electrical performance, with a turn-on voltage ∼2 V and negligible leakage current under reverse bias. The monolithic integration of full-color LEDs on a single chip, coupled with the capacity to tune light emission characteristics at the single nanowire level, provides an unprecedented approach to realize ultrasmall and efficient projection display, smart lighting, and on-chip spectrometer.

Rh/InGaN1-xOx nanoarchitecture for light-driven methane reforming with carbon dioxide toward syngas.

Light-driven dry reforming of methane toward syngas presents a proper solution for alleviating climate change and for the sustainable supply of transportation fuels and chemicals. Herein, Rh/InGaN1-xOx nanowires supported by silicon wafer are explored as an ideal platform for loading Rh nanoparticles, thus assembling a new nanoarchitecture for this grand topic. In combination with the remarkable photo-thermal synergy, the O atoms in Rh/InGaN1-xOx can significantly lower the apparent activation energy of dry reforming of methane from 2.96 eV downward to 1.70 eV. The as-designed Rh/InGaN1-xOx NWs nanoarchitecture thus demonstrates a measurable syngas evolution rate of 180.9 mmol gcat-1 h-1 with a marked selectivity of 96.3% under concentrated light illumination of 6 W cm-2. What is more, a high turnover number (TON) of 4182 mol syngas per mole Rh has been realized after six reuse cycles without obvious activity degradation. The correlative 18O isotope labeling experiments, in-situ irradiated X-ray photoelectron spectroscopy (ISI-XPS) and in-situ diffuse reflectance Fourier transform infrared spectroscopy characterizations, as well as density functional theory calculations reveal that under light illumination, Rh/InGaN1-xOx NWs facilitate releasing *CH3 and H+ from CH4 by holes, followed by H2 evolution from H+ reduction with electrons. Subsequently, the O atoms in Rh/InGaN1-xOx can directly participate in CO generation by reacting with the *C species from CH4 dehydrogenation and contributes to the coke elimination, in concurrent formation of O vacancies. The resultant O vacancies are then replenished by CO2, showing an ideal chemical loop. This work presents a green strategy for syngas production via light-driven dry reforming of methane.

Multi-metallic Layered Catalysts for Stable Electrochemical CO2 Reduction to Formate and Formic Acid.

Electrochemical CO2 reduction (ECR) to value-added products such as formate/formic acid is a promising approach for CO2 mitigation. Practical ECR requires long-term stability at industrially relevant reduction rates, which is challenging due to the rapid degradation of most catalysts at high current densities. Herein, we report the development of a bismuth (Bi) gas diffusion electrode on a polytetrafluoroethylene-based electrically conductive silver (Ag) substrate (Ag@Bi), which exhibits high Faradaic efficiency (FE) for formate of over 90 % in 1 M KOH and 1 M KHCO3 electrolytes. The catalyst also shows high selectivity of formic acid above 85 % in 1 M NaCl catholyte, which has a bulk pH of 2-3 during ECR, at current densities up to 300 mA cm-2. In 1 M KHCO3 condition, Ag@Bi maintains formate FE above 90 % for at least 500 hours at the current density of 100 mA cm-2. We found that the Ag@Bi catalyst degrades over time due to the leaching of Bi in the NaCl catholyte. To overcome this challenge, we deposited a layer of Ag nanoparticles on the surface of Ag@Bi to form a multi-layer Ag@Bi/Ag catalyst. This designed catalyst exhibits 300 hours of stability with FE for formic acid ≥70 % at 100 mA cm-2. Our work establishes a new strategy for achieving the operational longevity of ECR under wide pH conditions, which is critical for practical applications.

A semiconducting hybrid of RhOx/GaN@InGaN for simultaneous activation of methane and water toward syngas by photocatalysis.

Prior to the eventual arrival of carbon neutrality, solar-driven syngas production from methane steam reforming presents a promising approach to produce transportation fuels and chemicals. Simultaneous activation of the two reactants, i.e. methane and water, with notable geometric and polar discrepancy is at the crux of this important subject yet greatly challenging. This work explores an exceptional semiconducting hybrid of RhOx/GaN@InGaN nanowires for overcoming this critical challenge to achieve efficient syngas generation from methane steam reforming by photocatalysis. By coordinating density functional theoretical calculations and microscopic characterizations, with in situ spectroscopic measurements, it is found that the multifunctional RhOx/GaN interface is effective for simultaneously activating both CH4 and H2O by stretching the C-H and O-H bonds because of its unique Lewis acid/base attribute. With the aid of energetic charge carriers, the stretched C-H and O-H bonds of reactants are favorably cleaved, resulting in the key intermediates, i.e. *CH3, *OH, and *H, to sit on Rh sites, Rh sites, and N sites, respectively. Syngas is subsequently produced via energetically favored pathway without additional energy inputs except for light. As a result, a benchmarking syngas formation rate of 8.1 mol·gcat-1·h-1 is achieved with varied H2/CO ratios from 2.4 to 0.8 under concentrated light illumination of 6.3 W·cm-2, enabling the achievement of a superior turnover number of 10,493 mol syngas per mol Rh species over 300 min of long-term operation. This work presents a promising strategy for green syngas production from methane steam reforming by utilizing unlimited solar energy.

Oxynitride-surface engineering of rhodium-decorated gallium nitride for efficient thermocatalytic hydrogenation of carbon dioxide to carbon monoxide.

Upcycling of carbon dioxide towards fuels and value-added chemicals poses an opportunity to overcome challenges faced by depleting fossil fuels and climate change. Herein, combining highly controllable molecular beam epitaxy growth of gallium nitride (GaN) under a nitrogen-rich atmosphere with subsequent air annealing, a tunable platform of gallium oxynitride (GaN1-xOx) nanowires is built to anchor rhodium (Rh) nanoparticles for carbon dioxide hydrogenation. By correlatively employing various spectroscopic and microscopic characterizations, as well as density functional theory calculations, it is revealed that the engineered oxynitride surface of GaN works in synergy with Rh to achieve a dramatically reduced energy barrier. Meanwhile, the potential-determining step is switched from *COOH formation into *CO desorption. As a result, significantly improved CO activity of 127 mmol‧gcat-1‧h-1 is achieved with high selectivity of >94% at 290 °C under atmospheric pressure, which is three orders of magnitude higher than that of commercial Rh/Al2O3. Furthermore, capitalizing on the high dispersion of the Rh species, the architecture illustrates a decent turnover frequency of 270 mol CO per mol Rh per hour over 9 cycles of operation. This work presents a viable strategy for promoting CO2 refining via surface engineering of an advanced support, in collaboration with a suitable metal cocatalyst.

Diode-less bilayer oxide (WO(x)-NbO(x)) device for cross-point resistive memory applications.

The combination of a threshold switching device and a resistive switching (RS) device was proposed to suppress the undesired sneak current for the integration of bipolar RS cells in a cross-point array type memory. A simulation for this hybrid-type device shows that the matching of key parameters between switch element and memory element is an important issue. Based on the threshold switching oxides, a conceptual structure with a simple metal-oxide 1-oxide 2-metal stack was provided to accommodate the evolution trend. We show that electroformed W-NbO(x)-Pt devices can simultaneously exhibit both threshold switching and memory switching. A qualitative model was suggested to elucidate the unique properties in a W-NbO(x)-Pt stack, where threshold switching is associated with a localized metal-insulator transition in the NbO(x) bulk, and the bipolar RS derives from a redox at the tip of the localized filament at the WO(x)-NbO(x) interface. Such a simple metal-oxide-metal structure, with functionally separated bulk and interface effects, provides a fabrication advantage for future high-density cross-point memory devices.

Improved Performance of Electron Blocking Layer Free AlGaN Deep Ultraviolet Light-Emitting Diodes Using Graded Staircase Barriers.

To prevent electron leakage in deep ultraviolet (UV) AlGaN light-emitting diodes (LEDs), Al-rich p-type AlxGa(1-x)N electron blocking layer (EBL) has been utilized. However, the conventional EBL can mitigate the electron overflow only up to some extent and adversely, holes are depleted in the EBL due to the formation of positive sheet polarization charges at the heterointerface of the last quantum barrier (QB)/EBL. Subsequently, the hole injection efficiency of the LED is severely limited. In this regard, we propose an EBL-free AlGaN deep UV LED structure using graded staircase quantum barriers (GSQBs) instead of conventional QBs without affecting the hole injection efficiency. The reported structure exhibits significantly reduced thermal velocity and mean free path of electrons in the active region, thus greatly confines the electrons over there and tremendously decreases the electron leakage into the p-region. Moreover, such specially designed QBs reduce the quantum-confined Stark effect in the active region, thereby improves the electron and hole wavefunctions overlap. As a result, both the internal quantum efficiency and output power of the GSQB structure are ~2.13 times higher than the conventional structure at 60 mA. Importantly, our proposed structure exhibits only ~20.68% efficiency droop during 0-60 mA injection current, which is significantly lower compared to the regular structure.

An electrically pumped surface-emitting semiconductor green laser.

Surface-emitting semiconductor lasers have been widely used in data communications, sensing, and recently in Face ID and augmented reality glasses. Here, we report the first achievement of an all-epitaxial, distributed Bragg reflector (DBR)-free electrically injected surface-emitting green laser by exploiting the photonic band edge modes formed in dislocation-free gallium nitride nanocrystal arrays, instead of using conventional DBRs. The device operates at ~523 nm and exhibits a threshold current of ~400 A/cm2, which is over one order of magnitude lower compared to previously reported blue laser diodes. Our studies open a new paradigm for developing low-threshold surface-emitting laser diodes from the ultraviolet to the deep visible (~200 to 600 nm), wherein the device performance is no longer limited by the lack of high-quality DBRs, large lattice mismatch, and substrate availability.