Covalently Grafting Graphene onto Si Photocathode to Expedite Aqueous Photoelectrochemical CO2 Reduction.

Silicon semiconductor functionalized with molecular catalysts emerges as a promising cathode for photoelectrochemical (PEC) CO2 reduction reaction (CO2 RR). However, the limited kinetics and stabilities remains a major hurdle for the development of such composites. We herein report an assembling strategy of silicon photocathodes via chemically grafting a conductive graphene layer onto the surface of n+ -p Si followed by catalyst immobilization. The covalently-linked graphene layer effectively enhances the photogenerated carriers transfer between the cathode and the reduction catalyst, and improves the operating stability of the electrode. Strikingly, we demonstrate that altering the stacking configuration of the immobilized cobalt tetraphenylporphyrin (CoTPP) catalyst through calcination can further enhance the electron transfer rate and the PEC performance. At the end, the graphene-coated Si cathode immobilized with CoTPP catalyst managed to sustain a stable 1-Sun photocurrent of -1.65 mA cm-2 over 16 h for CO production in water at a near neutral potential of -0.1 V vs. reversible hydrogen electrode. This represents a remarkable improvement of PEC CO2 RR performance in contrast to the reported photocathodes functionalized with molecular catalysts.

Steering the Pathway of Plasmon-Enhanced Photoelectrochemical CO2 Reduction by Bridging Si and Au Nanoparticles through a TiO2 Interlayer.

Photoelectrochemical (PEC) conversion of CO2 in an aqueous medium into high-energy fuels is a creative strategy for storing solar energy and closing the anthropogenic carbon cycle. However, the rational design of catalytic architectures to selectively and efficiently produce a target product such as CO has remained a grand challenge. Herein, an efficient and selective Si photocathode for CO production is reported by utilizing a TiO2 interlayer to bridge the Au nanoparticles and n+ p-Si. The TiO2 interlayer can not only effectively protect and passivate Si surface, but can also exhibit outstanding synergies with Au nanoparticles to greatly promote CO2 reduction kinetics for CO production through stabilizing the key reaction intermediates. Specifically, the TiO2 layer and Au nanoparticles work concertedly to enhance the separation of localized surface plasmon resonance generated hot carriers, contributing to the improved activity and selectivity for CO production by utilizing the hot electrons generated in Au nanoparticles during PEC CO2 reduction. The optimized Au/TiO2 /n+ p-Si photocathode exhibits a Faradaic efficiency of 86% and a partial current density of -5.52 mA cm-2 at -0.8 VRHE for CO production, which represent state-of-the-art performance in this field. Such a plasmon-enhanced strategy may pave the way for the development of high-performance PEC photocathodes for energy-efficient CO2 utilization.

Silicon based photoelectrodes for photoelectrochemical water splitting.

Solar water splitting using Si photoelectrodes in photoelectrochemical (PEC) cells offers a promising approach to convert sunlight into sustainable hydrogen energy, which has recently received intense research. This review summarizes the recent advances in the development of efficient and stable Si photoelectrodes for solar water splitting. The definition and representation of efficiency and stability for Si photoelectrodes are firstly introduced. We then present several basic strategies for designing highly efficient and stable Si photoelectrodes, including surface textures, protective layer, catalyst loading and the integration of the system. Finally, we highlight the progress that has been made in Si photocathodes and Si photoanodes, respectively, with emphasis on how to integrate Si with protective layer and catalyst.

Enhanced Photoelectrochemical Performance in Reduced Graphene Oxide/BiFeO3 Heterostructures.

BiFeO3 (BFO)-based ferroelectrics have been proved to be visible-light-driven photoelectrodes for O2 production. However, the hitherto reported photoelectrochemical performances remain inferior to meet the requirements for any applications. Besides, expensive noble metals (Ag, Au) are commonly required to achieve high photoelectric conversion efficiency. Here, the significant enhancements of photoelectrochemical performance is reported by fabricating a noble-metal-free reduced graphene oxide (RGO)/BFO composite film via a simple and cost-effective solution process. The optimized RGO/BFO composite film exhibits a 600% improvement of the short-circuit photocurrent density compared to that of the pristine BFO, and also outperforms the noble-metal/BFO cells under the same reaction conditions. Furthermore, the incident photon-to-current efficiency of the optimized RGO/BFO sample shows threefold enhancement. This study delivers a facile and low-cost approach to preparing 2D materials/ferroelectric heterostructures and offers a promising pathway to boost the performance of semiconducting ferroelectric photoelectrodes.

Sulfidation-Induced Surface Local Electronic and Atomic Structures in a Silver Catalyst Enables Silicon Photocathode for Selective and Efficient Photoelectrochemical CO2 Reduction.

Converting CO2 to value-added chemicals through a photoelectrochemical (PEC) system is a creative approach toward renewable energy utilization and storage. However, the rational design of appropriate catalysts while being effectively integrated with semiconductor photoelectrodes remains a considerable challenge for achieving single-carbon products with high efficiency. Herein, we demonstrate a novel sulfidation-induced strategy for in situ grown sulfide-derived Ag nanowires on a Si photocathode (denoted as SD-Ag/Si) based on the standard crystalline Si solar cells. Such an exquisite design of the SD-Ag/Si photocathode not only provides a large electrochemically active surface area but also endows abundant active sites of Ag2S/Ag interfaces and high-index Ag facets for PEC CO production. The optimized SD-Ag/Si photocathode displays an ideal CO Faradic efficiency of 95.2% and an onset potential of +0.26 V versus the reversible hydrogen electrode, ascribed to the sulfidation-induced synergistic effect of the surface atomic arrangement and electronic structure in Ag catalysts that promote charge transfer, facilitate CO2 adsorption and activation, and suppress hydrogen evolution reaction. This sulfidation-induced strategy represents a scalable approach for designing high-performance catalysts for electrochemical and PEC devices with efficient CO2 utilization.

High-efficiency ferroelectric-film solar cells with an n-type Cu2O cathode buffer layer.

Because of the existence of interface Schottky barriers and depolarization electric field, ferroelectric films sandwiched between top and bottom electrodes are strongly expected to be used as a new kind of solar cells. However, the photocurrent with a typical order of µA/cm(2) is too low to be practical. Here we demonstrate that the insertion of an n-type cuprous oxide (Cu(2)O) layer between the Pb(Zr,Ti)O(3) (PZT) film and the cathode Pt contact in a ITO/PZT/Pt cell leads to the short-circuit photocurrent increasing 120-fold to 4.80 mA/cm(2) and power conversion efficiency increasing of 72-fold to 0.57% under AM1.5G (100 mW/cm(2)) illumination. Ultraviolet photoemission spectroscopy and dark J-V characteristic show an ohmic contact on Pt/Cu(2)O, an n(+)-n heterojunction on Cu(2)O/PZT and a Schottky barrier on PZT/ITO, which provide a favorable energy level alignment for efficient electron-extraction on the cathode. Our work opens up a promising new method that has the potential for fulfilling cost-effective ferroelectric-film photovoltaic.

Renewable formate from sunlight, biomass and carbon dioxide in a photoelectrochemical cell.

The sustainable production of chemicals and fuels from abundant solar energy and renewable carbon sources provides a promising route to reduce climate-changing CO2 emissions and our dependence on fossil resources. Here, we demonstrate solar-powered formate production from readily available biomass wastes and CO2 feedstocks via photoelectrochemistry. Non-precious NiOOH/α-Fe2O3 and Bi/GaN/Si wafer were used as photoanode and photocathode, respectively. Concurrent photoanodic biomass oxidation and photocathodic CO2 reduction towards formate with high Faradaic efficiencies over 85% were achieved at both photoelectrodes. The integrated biomass-CO2 photoelectrolysis system reduces the cell voltage by 32% due to the thermodynamically favorable biomass oxidation over conventional water oxidation. Moreover, we show solar-driven formate production with a record-high yield of 23.3 µmol cm-2 h-1 as well as high robustness using the hybrid photoelectrode system. The present work opens opportunities for sustainable chemical and fuel production using abundant and renewable resources on earth-sunlight, biomass and CO2.

Cupric porphyrin frameworks on multi-junction silicon photocathodes to expedite the kinetics of CO2 turnover.

Photoelectrochemical CO2 reduction utilizing silicon-based photocathodes offers a promising route to directly store solar energy in chemical bonds, provoking the development of heterogeneous molecular catalysts with high turnover rates. Herein, an in situ surface transformation strategy is adopted to grow metal-organic frameworks (MOFs) on Si-based photocathodes, serving as catalytic scaffolds for boosting both the kinetics and selectivity of CO2 reduction. Benefitting from the multi-junctional configuration for enhanced charge separation and the porous MOF scaffold enriching redox-active metalloporphyrin sites, the Si photocathode demonstrates a high CO faradaic efficiency of 87% at a photocurrent density of 10.2 mA cm-2, which is among the best seen for heterogeneous molecular catalysts. This study highlights the exploitation of reticular chemistry and macrocycle complexes as Earth-abundant alternatives for catalyzing artificial photosynthesis.

NiMoFe/Cu nanowire core-shell catalysts for high-performance overall water splitting in neutral electrolytes.

A bifunctional NiMoFe/Cu NW core-shell catalyst assembled into a practical solar-driven overall water splitting system leads to an unprecedented solar-to-hydrogen (STH) efficiency of 10.99% in neutral electrolytes, attributed to the synergic combination of a unique 3D self-supported core-shell architecture and rapid electron/mass transfer properties.

Scaling dopant states in a semiconducting nanostructure by chemically resolved electron energy-loss spectroscopy: a case study on Co-doped ZnO.

Dilute dopant introduces foreign states to the electronic structures of host semiconductors and imparts intriguing properties to the materials. Identifying and positioning the dopant states are of crucial importance for seeking the underlying mechanism in the doped systems. However, such determination has still been challenging, particularly for individual nanostructured materials, due to the lack of the spectroscopic probe that possesses both nanometer spatial resolution and chemical resolution. Here, we shall demonstrate the successful scaling of dopant states of individual semiconducting nanostructures by chemically resolved electron energy-loss spectroscopy (EELS), taking the individual Co-doped ZnO nanorods as an example. Guided by the Co dopant spatial distribution mapped by the core-loss EELS technique, chemical resolution is achieved in the accumulated valence electron energy-loss spectra. Three Co dopant states are successfully identified and positioned in the host ZnO bands. Furthermore, the electron extension degrees of the Co dopant states are assessed on the basis of the multiple-atom effect. The above experimental inputs optimize the density functional theoretical calculations, which generates the corrected full electronic structures of (Zn,Co)O dilute magnetic semiconductors. These results give a carrier-mediated interpretation for the room-temperature ferromagnetism of Co-doped ZnO nanostructures based on a recent theory.

Integration of Oxygen-Vacancy-Rich NiFe-Layered Double Hydroxide onto Silicon as Photoanode for Enhanced Photoelectrochemical Water Oxidation.

Photoelectrochemical (PEC) water splitting has the potential to efficiently convert intermittent solar energy into storable hydrogen fuel. However, poor charge separation and transfer ability as well as sluggish surface oxygen evolution reaction (OER) kinetics of the photoelectrode severely hinder the advance in PEC performance. Herein, a facile electrodeposition method was used to integrate Mo-doped NiFe-layered double hydroxide onto a NiOx /Ni-protected Si photoanode for enhanced PEC water oxidation. Mo doping contributed to an increased amount of oxygen vacancies, whereas a dynamic surface self-reconstruction was induced by Mo leaching under PEC OER conditions. This led to enhanced PEC performance with an onset potential of 0.87 V vs. reversible hydrogen electrode (RHE), a photocurrent density of 39.3 mA cm-2 at 1.23 V vs. RHE, a fill factor of 0.38, and a solar-to-oxygen conversion efficiency of 5.3 %, along with a stability of 130 h continuous PEC reaction. The performance was superior to that of the undoped NiFe-LDH/NiOx /Ni/Si (4.3 %), which was attributed to the elevated interface charge separation, fast charge transfer, and accelerated OER kinetics.

5.1% efficiency of Si photoanodes for photoelectrochemical water splitting catalyzed by porous NiFe (oxy)hydroxide converted from NiFe oxysulfide.

A porous NiFe (oxy)hydroxide catalyst fabricated on n+pp+-Si/Ni/NiOx, which is converted from an electrodeposited NiFe oxysulfide, allows a silicon photoanode for water splitting to hit a record 5.1% efficiency with good stability of up to 135 h under 40 mA cm-2 in 1.0 M NaOH.

A porous Ni-O/Ni/Si photoanode for stable and efficient photoelectrochemical water splitting.

Excellent photoelectrochemical activity was demonstrated for an easily prepared porous Ni-O/Ni/Si photoanode with an onset potential of 0.93 VRHE, a photocurrent of 39.7 mA cm-2 at 1.23 VRHE, an energy conversion efficiency of 3.2% and a stability above 100 h.

11.5% efficiency of TiO2 protected and Pt catalyzed n+np+-Si photocathodes for photoelectrochemical water splitting: manipulating the Pt distribution and Pt/Si contact.

A combination of hydrogen passivation, electroless deposition of a Pt catalyst and coating a TiO2 protective layer leads to an unprecedented 11.5% energy conversion efficiency and one-week stability of an n+np+-Si photocathode for solar water splitting.

Improved photocathodic performance in Pt catalyzed ferroelectric BiFeO3 films sandwiched by a porous carbon layer.

A porous carbon layer was inserted between a BiFeO3 film and a Pt catalyst for efficient solar water splitting. A photocathodic current density of -235.4 µA cm-2 at 0 V versus RHE and an onset potential of 1.19 V versus RHE were obtained under 100 mW cm-2 Xe-lamp illumination.

Efficient and Stable Silicon Photocathodes Coated with Vertically Standing Nano-MoS2 Films for Solar Hydrogen Production.

Water splitting in a photoelectrochemical cell, which converts sunlight into hydrogen energy, has recently received intense research. Silicon is suitable as a viable light-harvesting material for constructing such cell; however, there is a need to improve its stability and explore a cheap and efficient cocatalyst. Here we fabricate highly efficient and stable photocathodes by integrating crystalline MoS2 catalyst with ∼2 nm Al2O3 protected n+p-Si. Al2O3 acts as a protective and passivative layer of the Si surface, while the sputtering method using a MoS2 target along with a postannealing leads to a vertically standing, conformal, and crystalline nano-MoS2 layer on Al2O3/n+p-Si photocathode. Efficient (0.4 V vs RHE onset potential and 35.6 mA/cm2 saturated photocurrent measured under 100 mA/cm2 Xe lamp illumination) and stable (above 120 h continuous water splitting) photocathode was obtained, which opens the door for the MoS2 catalyst to be applied in photoelectrochemical hydrogen evolution in a facile and scalable way.

N-Doped nanodots/np(+)-Si photocathodes for efficient photoelectrochemical hydrogen generation.

Carbon nanodots treated with N2-plasma are effective catalysts for solar-driven hydrogen-evolved-reaction on np(+)-Si photocathodes and a support for Pt allowing for the reduction in Pt loading by a factor of about 3.5 while improving the photoelectrochemical activity.

The photocathodic properties of a Pb(Zr(0.2)Ti(0.8))O3 wrapped CaFe2O4 layer on ITO coated quartz for water splitting.

Pb(Zr(0.2)Ti(0.8))O3 wrapped CaFe2O4 particles were constructed on ITO coated quartz as a photocathode for efficient water splitting. A photocurrent of 152 µA cm(-2) was obtained under zero bias vs. Ag/AgCl and 100 mW cm(-2) with the assistance of positive poling and Ag decoration.

An equivalent realization of coherent perfect absorption under single beam illumination.

We have experimentally and numerically demonstrated that the coherent perfect absorption (CPA) can equivalently be accomplished under single beam illumination. Instead of using the counter-propagating coherent dual beams, we introduce a perfect magnetic conductor (PMC) surface as a mirror boundary to the CPA configuration. Such a PMC surface can practically be embodied, utilizing high impedance surfaces, i.e., mushroom structures. By covering them with an ultrathin conductive film of sheet resistance 377 Ω, the perfect (100%) microwave absorption is achieved when the film is illuminated by a single beam from one side. Employing the PMC boundary reduces the coherence requirement in the original CPA setup, though the present implementation is limited to the single frequency or narrow band operation. Our work proposes an equivalent way to realize the CPA under the single beam illumination, and might have applications in engineering absorbent materials.

Photovoltaic enhancement due to surface-plasmon assisted visible-light absorption at the inartificial surface of lead zirconate-titanate film.

PZT film of 300 nm thickness was deposited on tin indium oxide (ITO) coated quartz by a sol-gel method. Four metal electrodes, such as Pt, Au, Cu and Ag, were used as top electrodes deposited on the same PZT film by sputtering at room temperature. In ITO-PZT-Ag and ITO-PZT-Au structures, the visible light (400-700 nm) can be absorbed partially by a PZT film, and the maximum efficiency of photoelectric conversion of the ITO-PZT-Ag structure was enhanced to 0.42% (100 mW cm(-2), AM 1.5G), which is about 15 times higher than that of the ITO-PZT-Pt structure. Numerical simulations show that the natural random roughness of polycrystalline-PZT-metal interface can offer a possibility of coupling between the incident photons and SPs at the metal surface. The coincidence between the calculated SP properties and the measured EQE spectra reveals the SP origin of the photovoltaic enhancement in these ITO-PZT-metal structures, and the improved photocurrent output is caused by the enhanced optical absorption in the PZT region near the metal surface, rather than by the direct charge-transfer process between two materials.