Solar-to-hydrogen efficiency of more than 9% in photocatalytic water splitting.

Production of hydrogen fuel from sunlight and water, two of the most abundant natural resources on Earth, offers one of the most promising pathways for carbon neutrality1-3. Some solar hydrogen production approaches, for example, photoelectrochemical water splitting, often require corrosive electrolyte, limiting their performance stability and environmental sustainability1,3. Alternatively, clean hydrogen can be produced directly from sunlight and water by photocatalytic water splitting2,4,5. The solar-to-hydrogen (STH) efficiency of photocatalytic water splitting, however, has remained very low. Here we have developed a strategy to achieve a high STH efficiency of 9.2 per cent using pure water, concentrated solar light and an indium gallium nitride photocatalyst. The success of this strategy originates from the synergistic effects of promoting forward hydrogen-oxygen evolution and inhibiting the reverse hydrogen-oxygen recombination by operating at an optimal reaction temperature (about 70 degrees Celsius), which can be directly achieved by harvesting the previously wasted infrared light in sunlight. Moreover, this temperature-dependent strategy also leads to an STH efficiency of about 7 per cent from widely available tap water and sea water and an STH efficiency of 6.2 per cent in a large-scale photocatalytic water-splitting system with a natural solar light capacity of 257 watts. Our study offers a practical approach to produce hydrogen fuel efficiently from natural solar light and water, overcoming the efficiency bottleneck of solar hydrogen production.

Crystallographic Effects of GaN Nanostructures in Photoelectrochemical Reaction.

Tuning the surface structure of the photoelectrode provides one of the most effective ways to address the critical challenges in artificial photosynthesis, such as efficiency, stability, and product selectivity, for which gallium nitride (GaN) nanowires have shown great promise. In the GaN wurtzite crystal structure, polar, semipolar, and nonpolar planes coexist and exhibit very different structural, electronic, and chemical properties. Here, through a comprehensive study of the photoelectrochemical performance of GaN photocathodes in the form of films and nanowires with controlled surface polarities we show that significant photoelectrochemical activity can be observed when the nonpolar surfaces are exposed in the electrolyte, whereas little or no activity is measured from the GaN polar c-plane surfaces. The atomic origin of this fundamental difference is further revealed through density functional theory calculations. This study provides guideline on crystal facet engineering of metal-nitride photo(electro)catalysts for a broad range of artificial photosynthesis chemical reactions.

CuS-Decorated GaN Nanowires on Silicon Photocathodes for Converting CO2 Mixture Gas to HCOOH.

Hybrid materials consisting of semiconductors and cocatalysts have been widely used for photoelectrochemical (PEC) conversion of CO2 gas to value-added chemicals such as formic acid (HCOOH). To date, however, the rational design of catalytic architecture enabling the reduction of real CO2 gas to chemical has remained a grand challenge. Here, we report a unique photocathode consisting of CuS-decorated GaN nanowires (NWs) integrated on planar silicon (Si) for the conversion of H2S-containing CO2 mixture gas to HCOOH. It was discovered that H2S impurity in the modeled industrial CO2 gas could lead to the spontaneous transformation of Cu to CuS NPs, which resulted in significantly increased faradaic efficiency of HCOOH generation. The CuS/GaN/Si photocathode exhibited superior faradaic efficiency of HCOOH = 70.2% and partial current density = 7.07 mA/cm2 at -1.0 VRHE under AM1.5G 1 sun illumination. To our knowledge, this is the first demonstration that impurity mixed in the CO2 gas can enhance, rather than degrade, the performance of the PEC CO2 reduction reaction.

Water-promoted selective photocatalytic methane oxidation for methanol production.

Converting relatively inert methane into active chemical fuels such as methanol with high selectivity through an energy-saving strategy has remained a grand challenge. Photocatalytic technology consuming solar energy is an appealing alternative for methane reforming. However, the low efficiency and the undesirable formation of low-value products, such as carbon dioxide and ethane, limit the commercial application of photocatalytic technology. Herein, we find a facile and practical water-promoted pathway for photocatalytic methane reforming into methanol, enabling methanol production from methane and oxygen with a high selectivity (>93%) and production rate (21.4 µmol cm-2 h-1 or 45.5 mmol g-1 h-1) on metallic Ag nanoparticle-loaded InGaN nanowires (Ag/InGaN). The experimental XPS and theoretical PDOS analyses reveal that water molecules adsorbed on Ag nanoparticles (AgNPs) can promote the electron transfer from InGaN to AgNPs, which enables the formation of partial Ag species with a lower oxidation state in AgNPs. Through the in situ IR spectrum and the reaction pathway simulation studies, these newly formed Ag species induced by water adsorption were demonstrated to be responsible for the highly selective methanol production due to the effective formation of a C-O bond and the optimal desorption of the formed methanol from the surface indium site of the InGaN photocatalyst. This unique water promotion effect leads to a 55-fold higher catalytic rate and 9-fold higher selectivity for methanol production compared to photocatalytic methane reforming without water addition. This finding offers a new pathway for achieving clean solar fuels by photocatalysis-based methane reforming.

Concentrated Solar Light Photoelectrochemical Water Splitting for Stable and High-Yield Hydrogen Production.

Photoelectrochemical water splitting is a promising technique for converting solar energy into low-cost and eco-friendly H2 fuel. However, the production rate of H2 is limited by the insufficient number of photogenerated charge carriers in the conventional photoelectrodes under 1 sun (100 mW cm-2) light. Concentrated solar light irradiation can overcome the issue of low yield, but it leads to a new challenge of stability because the accelerated reaction alters the surface chemical composition of photoelectrodes. Here, it is demonstrated that loading Pt nanoparticles (NPs) on single crystalline GaN nanowires (NWs) grown on n+-p Si photoelectrode operates efficiently and stably under concentrated solar light. Although a large number of Pt NPs detach during the initial reaction due to H2 gas bubbling, some Pt NPs which have an epitaxial relation with GaN NWs remain stably anchored. In addition, the stability of the photoelectrode further improves by redepositing Pt NPs on the reacted Pt/GaN surface, which results in maintaining onset potential >0.5 V versus reversible hydrogen electrode and photocurrent density >60 mA cm-2 for over 1500 h. The heterointerface between Pt cocatalysts and single crystalline GaN nanostructures shows great potential in designing an efficient and stable photoelectrode for high-yield solar to H2 conversion.

Pt nanoclusters on GaN nanowires for solar-asssisted seawater hydrogen evolution.

Seawater electrolysis provides a viable method to produce clean hydrogen fuel. To date, however, the realization of high performance photocathodes for seawater hydrogen evolution reaction has remained challenging. Here, we introduce n+-p Si photocathodes with dramatically improved activity and stability for hydrogen evolution reaction in seawater, modified by Pt nanoclusters anchored on GaN nanowires. We find that Pt-Ga sites at the Pt/GaN interface promote the dissociation of water molecules and spilling H* over to neighboring Pt atoms for efficient H2 production. Pt/GaN/Si photocathodes achieve a current density of -10 mA/cm2 at 0.15 and 0.39 V vs. RHE and high applied bias photon-to-current efficiency of 1.7% and 7.9% in seawater (pH = 8.2) and phosphate-buffered seawater (pH = 7.4), respectively. We further demonstrate a record-high photocurrent density of ~169 mA/cm2 under concentrated solar light (9 suns). Moreover, Pt/GaN/Si can continuously produce H2 even under dark conditions by simply switching the electrical contact. This work provides valuable guidelines to design an efficient, stable, and energy-saving electrode for H2 generation by seawater splitting.

Oxynitrides enabled photoelectrochemical water splitting with over 3,000 hrs stable operation in practical two-electrode configuration.

Solar photoelectrochemical reactions have been considered one of the most promising paths for sustainable energy production. To date, however, there has been no demonstration of semiconductor photoelectrodes with long-term stable operation in a two-electrode configuration, which is required for any practical application. Herein, we demonstrate the stable operation of a photocathode comprising Si and GaN, the two most produced semiconductors in the world, for 3,000 hrs without any performance degradation in two-electrode configurations. Measurements in both three- and two-electrode configurations suggest that surfaces of the GaN nanowires on Si photocathode transform in situ into Ga-O-N that drastically enhances hydrogen evolution and remains stable for 3,000 hrs. First principles calculations further revealed that the in-situ Ga-O-N species exhibit atomic-scale surface metallization. This study overcomes the conventional dilemma between efficiency and stability imposed by extrinsic cocatalysts, offering a path for practical application of photoelectrochemical devices and systems for clean energy.

Metal-Support Interaction-Promoted Photothermal Catalytic Methane Reforming into Liquid Fuels.

Clean and renewable photocatalytic technology for methane reforming into high-value liquid fuels, such as methanol, is a promising strategy for commercial industrial applications. However, poor charge separation, sluggish methane activation, and excessive oxidation collectively inhibit the production of methanol from photocatalytic methane reforming. Herein, we have developed enhanced metal-support interactions between a GaN nanowire photocatalyst and a Cu nanoparticle (CuNP) cocatalyst via p-doping in GaN. CuNP-loaded p-type GaN (Cu/p-GaN) with enhanced metal-support interaction has 3.5-fold higher activity (12.8 mmol g-1 h-1, higher than previous reports) for methanol production in photothermal catalytic methane reforming with oxygen as an oxidant and sunlight as the sole energy source than CuNP-loaded intrinsic GaN (Cu/i-GaN) or n-type GaN (Cu/n-GaN). In-situ IR measurements indicate that enhanced metal-support interaction significantly promotes activation of methane and formation of methanol. Combining with X-ray photoelectron spectroscopy (XPS), density functional theory (DFT) simulations demonstrate that this enhanced metal-support interaction in Cu/p-GaN greatly improves electron transfer from p-GaN photocatalysts to the 3d states of CuNP cocatalysts through the interface between them. Catalytic pathway simulations further reveal that the enhanced metal-support interaction in Cu/p-GaN also desirably decreases the reaction energy of rate-determining methanol desorption, which decreases the excessive oxidation of the produced methanol and accelerates the regeneration of surface catalytic sites. These studies and findings offer critical insights into the design and development of metal nanoparticle-loaded photocatalysts for photocatalysis-based methane reforming into methanol.

Thermal transport characterization of carbon and silicon doped stanene nanoribbon: an equilibrium molecular dynamics study.

Equilibrium molecular dynamics simulation has been carried out for the thermal transport characterization of nanometer sized carbon and silicon doped stanene nanoribbon (STNR). The thermal conduction properties of doped stanene nanostructures are yet to be explored and hence in this study, we have investigated the impact of carbon and silicon doping concentrations as well as doping patterns namely single doping, double doping and edge doping on the thermal conductivity of nanometer sized zigzag STNR. The room temperature thermal conductivities of 15 nm × 4 nm doped zigzag STNR at 2% carbon and silicon doping concentration are computed to be 9.31 ± 0.33 W m-1 K-1 and 7.57 ± 0.48 W m-1 K-1, respectively whereas the thermal conductivity for the pristine STNR of the same dimension is calculated as 1.204 ± 0.21 W m-1 K-1. We find that the thermal conductivity of both carbon and silicon doped STNR increases with the increasing doping concentration for both carbon and silicon doping. The magnitude of increase in STNR thermal conductivity due to carbon doping has been found to be greater than that of silicon doping. Different doping patterns manifest different degrees of change in doped STNR thermal conductivity. Double doping pattern for both carbon and silicon doping induces the largest extent of enhancement in doped STNR thermal conductivity followed by single doping pattern and edge doping pattern respectively. The temperature and width dependence of doped STNR thermal conductivity has also been studied. For a particular doping concentration, the thermal conductivity of both carbon and silicon doped STNR shows a monotonic decaying trend at elevated temperatures while an opposite pattern is observed for width variation i.e. thermal conductivity increases with the increase in ribbon width. Such comprehensive study on doped stanene would encourage further investigation on the proper optimization of thermal transport characteristics of stanene nanostructures and provide deep insight in realizing the potential application of doped STNR in thermoelectric as well as thermal management of stanene based nanoelectronic devices.