Constructing a AZO/TiO2 Core/Shell Nanocone Array with Uniformly Dispersed Au NPs for Enhancing Photoelectrochemical Water Splitting

Constructing core/shell nanostructures with optimal structure and composition could maximize the solar light utilization. Here, using an Al nanocone array as a substrate, a well‐defined regular array of AZO/TiO₂ core/shell nanocones with uniformly dispersed Au nanoparticles (AZO/TiO₂/Au NCA) is successfully realized through three sequential steps of atomic layer deposition, physical vapor deposition, and annealing processes. By tuning the structural and compositional parameters, the advantages of light trapping and short carrier diffusion from the core/shell nanocone array, as well as the surface plasmon resonance and catalytic effects from the Au nanoparticles can be maximally utilized. Accordingly, a remarkable photoelectrochemical (PEC) performance can be acquired and the photocurrent density of the AZO/TiO₂/Au NCA electrode reaches up to 1.1 mA cm^?2 at 1.23 V, versus reversible hydrogen electrode (RHE) under simulated sunlight illumination, which is five times that of a flat AZO/TiO₂ electrode (0.22 mA cm^?2). Moreover, the photoconversion of the AZO/TiO₂/Au NCA electrode approaches 0.73% at 0.21 V versus RHE, which is one of the highest values with the lowest applied bias ever reported in Au/TiO₂ PEC composites. These results demonstrate a feasible route toward the scalable fabrication of well‐modulated core/shell nanostructures and can be easily applied to other metal/semiconductor composites for high‐performance PEC.     

Exceptional Visible‐Light‐Driven Cocatalyst‐Free Photocatalytic Activity of g‐C3N4 by Well Designed Nanocomposites with Plasmonic Au and SnO2

In this work, plasmonic Au/SnO₂/g‐C₃N₄ (Au/SO/CN) nanocomposites have been successfully synthesized and applied in the H₂ evolution as photocatalysts, which exhibit superior photocatalytic activities and favorable stability without any cocatalyst under visible‐light irradiation. The amount‐optimized 2Au/6SO/CN nanocomposite capable of producing approximately 770 μmol g^?1 h^?1 H₂ gas under λ > 400 nm light illumination far surpasses the H₂ gas output of SO/CN (130 μmol g^?1), Au/CN (112 μmol g^?1 h^?1), and CN (11 μmol g^?1 h^?1) as a contrast. In addition, the photocatalytic activity of 2Au/6SO/CN maintains unchanged for 5 runs in 5 h. The enhanced photoactivity for H₂ evolution is attributed to the prominently promoted photogenerated charge separation via the excited electron transfer from plasmonic Au (≈520 nm) and CN (470 nm > λ > 400 nm) to SO, as indicated by the surface photovoltage spectra, photoelectrochemical I–V curves, electrochemical impedance spectra, examination of formed hydroxyl radicals, and photocurrent action spectra. Moreover, the Kelvin probe test indicates that the newly aligned conduction band of SO in the fabricated 2Au/6SO/CN is indispensable to assist developing a proper energy platform for the photocatalytic H₂ evolution. This work distinctly provides a feasible strategy to synthesize highly efficient plasmonic‐assisted CN‐based photocatalysts utilized for solar fuel production.     

Enhancing Mo:BiVO4 Solar Water Splitting with Patterned Au Nanospheres by Plasmon‐Induced Energy Transfer

Plasmonic metal nanostructures have been extensively investigated to improve the performance of metal oxide photoanodes for photoelectrochemical (PEC) solar water splitting cells. Most of these studies have focused on the effects of those metal nanostructures on enhancing light absorption and enabling direct energy transfer via hot electrons. However, several recent studies have shown that plasmonic metal nanostructures can improve the PEC performance of metal oxide photoanodes via another mechanism known as plasmon‐induced resonant energy transfer (PIRET). However, this PIRET effect has not yet been tested for the molybdenum‐doped bismuth vanadium oxide (Mo:BiVO₄), regarded as one of the best metal oxide photoanode candidates. Here, this study constructs a hybrid Au nanosphere/Mo:BiVO₄ photoanode interwoven in a hexagonal pattern to investigate the PIRET effect on the PEC performance of Mo:BiVO₄. This study finds that the Au nanosphere array not only increases light absorption of the photoanode as expected, but also improves both its charge transport and charge transfer efficiencies via PIRET, as confirmed by time‐correlated single photon counting and transient absorption studies. As a result, incorporating the Au nanosphere array increases the photocurrent density of Mo:BiVO₄ at 1.23 V versus RHE by ≈2.2‐fold (2.83 mA cm^?2).     

Boosting Photoelectrochemical Water Splitting by TENG‐Charged Li‐Ion Battery

The need for cost‐effective and sustainable power supplies has spurred a growing interest in hybrid energy harvesting systems, and the most elementary energy production process relies on intermittent solar power. Here, it is shown how the ambient mechanical energy leads to water splitting in a photoelectrochemical (PEC) cell boosted by a triboelectric nanogenerator (TENG). In this strategy, a flexible TENG collects and transforms mechanical energy into electric current, which boosts the PEC water splitting via the charged Li‐ion battery. Au nanoparticles are deposited on TiO₂ nanoarrays for extending the available light spectrum to visible part by surface plasmon resonance effect, which yields a photocurrent density of 1.32 mA cm^?2 under AM 1.5 G illumination and 0.12 mA cm^?2 under visible light with a bias of 0.5 V. The TENG‐charged battery boosts the water splitting performance through coupling electrolysis and enhanced electron–hole separation efficiency. The hybrid cell exhibits an instantaneous current more than 9 mA with a working electrode area of 0.3 cm², suggesting a simple but efficient route for simultaneously converting solar radiation and mechanical energy into hydrogen.     

Vertical CoP Nanoarray Wrapped by N,P‐Doped Carbon for Hydrogen Evolution Reaction in Both Acidic and Alkaline Conditions

Hydrogen evolution reaction (HER) is a key reaction in water splitting, and developing efficient and robust non‐noble electrocatalysts for HER is still a great challenge for large‐scale hydrogen production. Herein, a vertically aligned core–shell structure grown on Ti foil with CoP nanoarray as a core and N,P‐doped carbon (NPC) as a shell (CoP/NPC/TF) is first reported as an efficient electrocatalyst for HER. Results indicate that CoP/NPC/TF only demands the overpotentials of 91 and 80 mV to drive the current density of 10 mA cm^?2 in acidic and alkaline solutions. The electrochemical measurements and theoretical calculations show that the synergy of CoP nanorod core and porous NPC shell enhances HER performance significantly, because the introduction of porous NPC shell not only offers more active sites but also improves the electrical conductivity and durability of the sample in acidic and alkaline solutions. Density functional theory calculation further reveals that all the C atoms between N and P atoms in CoP/NPC are the most efficient active sites, which greatly improve the HER performance. The identification of active species in this work provides an effective strategy to design and synthesize the low‐cost, high‐efficient, and robust CoP‐based electrocatalysts.     

Near‐Infrared,Heavy Metal‐Free Colloidal “Giant” Core/Shell Quantum Dots

“Giant” core/shell quantum dots (g‐QDs) are a promising class of materials for future optoelectronic technologies due to their superior chemical‐ and photostability compared to bare QDs and core/thin shell QDs. However, inadequate light absorption in the visible and near‐infrared (NIR) region and frequent use of toxic heavy metals (e.g., Cd and Pb) are still major challenges for most g‐QDs (e.g., CdSe/CdS) synthesized to date. The synthesis of NIR, heavy metal‐free, Zn‐treated spherical CuInSe₂/CuInS₂ g‐QDs is reported using the sequential cation exchange method. These g‐QDs exhibit tunable NIR optical absorption and photoluminescence (PL) properties. Transient fluorescence spectroscopy shows prolonged lifetime with increasing shell thickness, indicating the formation of quasi type‐II band alignment, which is further confirmed by simulations. As a proof‐of‐concept, as‐synthesized g‐QDs are used to sensitize TiO₂ as a photoanode in a photoelectrochemical (PEC) cell, demonstrating an efficient and stable PEC system. These results pave the way toward synthesizing NIR heavy metal‐free g‐QDs, which are very promising components of future optoelectronic technologies.     

Over 17% Efficiency Stand‐Alone Solar Water Splitting Enabled by Perovskite‐Silicon Tandem Absorbers

Realizing solar‐to‐hydrogen (STH) efficiencies close to 20% using low‐cost semiconductors remains a major step toward accomplishing the practical viability of photoelectrochemical (PEC) hydrogen generation technologies. Dual‐absorber tandem cells combining inexpensive semiconductors are a promising strategy to achieve high STH efficiencies at a reasonable cost. Here, a perovskite photovoltaic biased silicon (Si) photoelectrode is demonstrated for highly efficient stand‐alone solar water splitting. A p⁺nn⁺ ‐Si/Ti/Pt photocathode is shown to present a remarkable photon‐to‐current efficiency of 14.1% under biased condition and stability over three days under continuous illumination. Upon pairing with a semitransparent mixed perovskite solar cell of an appropriate bandgap with state‐of‐the‐art performance, an unprecedented 17.6% STH efficiency is achieved for self‐driven solar water splitting. Modeling and analysis of the dual‐absorber PEC system reveal that further work into replacing the noble‐metal catalyst materials with earth‐abundant elements and improvement of perovskite fill factor will pave the way for the realization of a low‐cost high‐efficiency PEC system.     

Influence of Anisotropy on Optical Bistability in Plasmonic Nanoparticles with Cylindrical Symmetry

In this paper, the effect of radial anisotropy on optical bistability in the cylindrical nanoshells is theoretically investigated within the quasi-static approximation. We consider two cases: when the shell is anisotropic and the core is nonlinear metal and when the core is anisotropic and the shell is a nonlinear metal. The dependence of optical bistability on the size of the nonlinear/anisotropic shell or core, the embedding medium, the anisotropy parameter, and the type of noble metals as candidates for plasmonics is studied and demonstrated. We show that by changing the type of the plasmonic metal, the switching threshold field changes can be used to design nanoparticle-based all-optical sensors. It is also shown that significant optical bistability and all-optical switching behavior can be obtained in the cylindrical nanoshells due to nonlinearity enhancement via the plasmonic structure.     

Ultrafast All‐Solid‐State Coaxial Asymmetric Fiber Supercapacitors with a High Volumetric Energy Density

Fiber‐supercapacitors (FSCs) are promising energy storage devices that can complement or even replace microbatteries in miniaturized portable and wearable electronics. Currently, a major challenge for FSCs is achieving ultrahigh volumetric energy and power densities simultaneously, especially when the charge/discharge rates exceed 1 V s^?1. Herein, an Au‐nanoparticle‐doped‐MnO_x@CoNi‐alloy@carbon‐nanotube (Au–MnO_x@CoNi@CNT) core/shell nanocomposite fiber electrode is designed, aiming to boost its charge/discharge rate by taking advantage of the superconductive CoNi alloy network and the greatly enhanced conductivity of the Au doped MnO_x active materials. An all‐solid‐state coaxial asymmetric FSC (CAFSC) prototype device made by wrapping this fiber with a holey graphene paper (HGP) exhibits excellent performance at rates up to 10 V s^?1, which is the highest charge rate demonstrated so far for FSCs based on pseudocapacitive materials. Furthermore, our fully packaged CAFSC delivers a volumetric energy density of ≈15.1 mW h cm^?3, while simultaneously maintaining a high power density of 7.28 W cm^?3 as well as a long cycle life (90% retention after 10 000 cycles). This value is the highest among all reported FSCs, even better than that of a typical 4 V/500 µA h thin‐film lithium battery.     

The “Midas Touch” Transformation of TiO2 Nanowire Arrays during Visible Light Photoelectrochemical Performance by Carbon/Nitrogen Coimplantation

Titanium dioxide is a promising photoanode material for water oxidation, but it is substantially limited by its poor efficiency in the visible light range. Herein, an innovative carbon/nitrogen coimplantation method is utilized to realize the “Midas touch” transformation of TiO₂ nanowire (NW) arrays for photoelectrochemical (PEC) water splitting in visible light. These modified golden–yellow rutile TiO₂ NW arrays (C/N‐TiO₂) exhibit remarkably enhanced absorption in visible light regions and more efficient charge separation and transfer. As a result, the photocurrent density of carbon/nitrogen co‐implanted TiO₂ under visible light (>420 nm) can reach 0.76 mA cm^?2, which far exceeds the value of 3 µA cm^?2 seen for pristine TiO₂ nanowire arrays at 0.8 V versus Ag/AgCl. An incident photon to electron conversion efficiency of ≈14.8% is achieved at 450 nm on C/N‐TiO₂ without any other cocatalysts. The ion implantation doping approach, combined with codoping strategies, is proved to be an effective strategy for enhancing the photoelectrochemical conversion and can enable further improvement of the PEC water‐splitting performance of many other semiconductor photoelectrodes.     

Facile and Efficient Atomic Hydrogenation Enabled Black TiO2 with Enhanced Photo‐Electrochemical Activity via a Favorably Low‐Energy‐Barrier Pathway

Black TiO₂ has demonstrated a great potential for a variety of renewable energy technologies. However, its practical application is heavily hindered due to lack of efficient hydrogenation methods and a deeper understanding of hydrogenation mechanisms. Here, a simple and straightforward hot wire annealing (HWA) method is presented to prepare black TiO₂ (H–TiO₂) nanorods with enhanced photo‐electrochemical (PEC) activity by means of atomic hydrogen [H]. Compared to conventional molecular hydrogen approaches, the HWA shows remarkable effectiveness without any detrimental side effects on the device structure, and simultaneously the photocurrent density of H–TiO₂ reaches 2.5 mA cm^?2 (at 1.23 V vs reversible hydrogen electrode (RHE)). Due to the controllable and reproducible [H] flux, the HWA can be developed as a standard hydrogenation method for black TiO₂. Meanwhile, the relationships between the wire temperatures, structural, optical, and photo‐electrochemical properties are systematically investigated to verify the improved PEC activity. Furthermore, the density functional theory (DFT) study provides a comprehensive insight not only into the highly efficient mechanism of the HWA approach but also its favorably low‐energy‐barrier hydrogenation pathway. The findings will have a profound impact on the broad energy applications of H–TiO₂ and contribute to the fundamental understanding of its hydrogenation.     

A Triphasic Bifunctional Oxygen Electrocatalyst with Tunable and Synergetic Interfacial Structure for Rechargeable Zn‐Air Batteries

Atomic‐scale design of interfacial structure is an intriguing but challenging approach to developing efficient heterogenous catalysts for bifunctional oxygen electrocatalysis. Herein, an exquisite triphasic interfacial structure featuring the encapsulation of Fe_xNi alloy in a graphitic shell with a partial exposure of the FeO_y thin‐layered surface is manipulated via an electronic modulation strategy. The spontaneous integration of well‐crystallized metal alloy, carbon shell with a tunable active FeO_y layer, not only guarantees smooth charge transfer across the thin oxide layer, but also generates the synergistic effect at the interface, thus dramatically boosting the intrinsic activity of oxygen catalysis. Benefiting from these attributes, the hybrid catalyst outperforms the commercial noble‐metal benchmarks with a higher half‐wave potential of 0.890 V for oxygen reduction reaction and lower overpotential of 308 mV at 10 mA cm^?2 for the oxygen evolution reaction in alkaline media. Beyond that, a high‐performance rechargeable Zn‐air battery is realized with a narrow voltage gap of 0.742 V and excellent cyclability over 500 cycles at 10 mA cm^?2, demonstrating the great potential of the as‐developed triphasic electrocatalyst for practical applications.     

Exploring Advanced Sandwiched Arrays by Vertical Graphene and N‐Doped Carbon for Enhanced Sodium Storage

Smart hybridization of active materials into tailored electrode structure is highly important for developing advanced electrochemical energy storage devices. With the help of sandwiched design, herein a powerful strategy is developed to fabricate three‐layer sandwiched composite core/shell arrays via combined hydrothermal and polymerization approaches. In such a unique architecture, wrinkled MoSe₂ nanosheets are sandwiched by vertical graphene (VG) core and N‐doped carbon (N‐C) shell forming sandwiched core/shell arrays. Interesting advantages including high electrical conductivity, strong mechanical stability, and large porosity are combined in the self‐supported VG/MoSe₂/N‐C sandwiched arrays. As a preliminary test, the sodium ion storage properties of VG/MoSe₂/N‐C sandwiched arrays are characterized and demonstrated with high capacity (540 mA h g^?1), enhanced high rate capability, and long‐term cycling stability (298 mA h g^?1 at 2.0 A g^?1 after 1000 cycles). The sandwiched core/shell structure plays positive roles in the enhancement of electrochemical performances due to dual conductive carbon networks, good volume accommodation, and highly porous structure with fast ion diffusion. The directional electrode design protocol provides a general method for synthesis of high‐performance ternary core/shell electrodes.     

Substrate-Independent Lattice Plasmon Modes for High-Performance On-Chip Plasmonic Sensors

We systematically study the lattice plasmon resonance structures, which are known as core/shell SiO₂/Au nanocylinder arrays (NCAs), for high-performance, on-chip plasmonic sensors using the substrate-independent lattice plasmon modes (LPMs). Our finite-difference time-domain simulations reveal that new modes of localized surface plasmon resonances (LSPRs) show up when the height-diameter aspect ratio of the NCAs is increased. The height-induced LSPRs couple with the superstrate diffraction orders to generate the substrate-independent LPMs. Moreover, we show that the high wavelength sensitivity and the narrow linewidth of the substrate-independent LPMs lead to the plasmonic sensors with high figure of merit (FOM) and high signal-to-noise ratio (SNR). In addition, the plasmonic sensors are robust in asymmetric environments for a wide range of working wavelengths. Our further study of both far- and near-field electromagnetic distribution in the NCAs confirms the height-enabled tunability of the plasmonic “hot spots” at the sub-nanoparticle resolution and the large field enhancement in the substrate-independent LPMs, which are responsible for the high FOM and SNR of the plasmonic sensors.     

Heat Diffusion‐Induced Gradient Energy Level in Multishell Bisulfides for Highly Efficient Photocatalytic Hydrogen Production

Insufficient light absorption and low carrier separation/transfer efficiency constitute two key issues that hinder the development of efficient photocatalytic hydrogen production. Here, multishell ZnS/CoS₂ bisulfide microspheres with gradient distribution of Zn based on the heat diffusion theory are designed. The Zn distribution can be adjusted by regulating the heating rate and manipulating the diffusion coefficients of the different elements conforming the multishell photocatalyst. Because of the unique structure, a gradient energy level is created from the core to the exterior of the multishell microspheres, which effectively facilitates the exciton separation and electron transfer. In addition, stronger light absorption and larger specific surface area have been achieved in the multishell ZnS/CoS₂ photocatalysts. As a result, the multishell ZnS/CoS₂ microspheres with gradient distribution of Zn exhibit a remarkable hydrogen production rate of 8001 µ mol g^?1 h^?1, which is 3.5 times higher than that of the normal multishell ZnS/CoS₂ particles with well‐distributed Zn and 11.3 times higher than that of the mixed nonshell ZnS and CoS₂ particles. This work demonstrates for the first time that controlling the diffusion rate of the different elements in the semiconductor is an effective route to simultaneously regulate morphology and structure to design highly efficient photocatalysts.     

Recent Advancement of p‐ and d‐Block Elements,Single Atoms,and Graphene‐Based Photoelectrochemical Electrodes for Water Splitting

Solar‐assisted photoelectrochemical (PEC) water splitting to produce hydrogen energy is considered the most promising solution for clean, green, and renewable sources of energy. For scaled production of hydrogen and oxygen, highly active, robust, and cost‐effective PEC electrodes are required. However, most of the available semiconductors as a PEC electrodes have poor light absorption, material degradation, charge separation, and transportability, which result in very low efficiency for photo‐water splitting. Generally, a promising photoelectrode is obtained when the surface of the semiconductor is modified/decorated with a suitable co‐catalyst because it increases the light absorbance spectrum and prevents electron–hole recombination during photoelectrode reactions. In this regard, numerous p‐ and d‐block elements, single atoms, and graphene‐based PEC electrodes have been widely used as semiconductor/co‐catalyst junctions to boost the performances of PEC overall water splitting. This review enumerates the recent progress and applications of p‐ and d‐block elements, single atoms, and graphene‐based PEC electrodes for water splitting. The focus is placed on fundamental mechanism, efficiency, cells design, and various aspects that contribute to the large‐scale prototype device. Finally, future perspectives, summary, challenges, and outlook for improving the activity of PEC photoelectrodes toward whole‐cell water splitting are addressed.     

Ligand-functionalized core/shell Ag@Au nanoparticles label-free amperometric immun-biosensor

A novel label-free electrochemical immunoassay based on core/shell Ag@Au nanoparticles monolayer as sensing interface has been developed for probing IgG. Several coupling techniques, such as Ag nanoparticles, Au nanoparticles, and the core/shell Ag@Au nanoparticles with L-Cysteine (Cys) cross-linking, were investigated for the determination of IgG and a very good result was obtained with the core/shell Ag@Au nanoparticles coupling. With the core/shell Ag@Au nanoparticles coupling method, the effects of the incubation time and pH on amperometric responses of the immunoassay were studied. The strong attachment of the cross-linked complex to the core/shell Ag@Au nanoparticles surface resulted in an excellent storage lifetime of 33 days. A dynamic concentration range of 2.3 to 960 ng/mL with a detection limit of 10 ng/mL was observed. Analytical results of 30 human serum samples obtained using the developing technique are in satisfactory agreement with those given by ELISA. In addition, it presents some superior advantages over the traditional sandwich format in that the analyzing performances are direct, rapid, and simple without multiple separation and labeling steps.     

CdSe and CdSe/CdS core–shell QDs: New approach for synthesis,investigating optical properties and application in pollutant degradation

In this work, CdSe quantum dots (QDs) were synthesized by a simple and rapid microwave activated approach using CdSO₄, Na₂SeO₃ as precursors and thioglycolic acid (TGA) as capping agent molecule. A novel photochemical approach was introduced for the growth of CdS QDs and this approach was used to grow a CdS shell around CdSe cores for the formation of a CdSe/CdS core–shell structure. The core–shells were structurally verified using X‐ray diffraction, transmission electron microscopy and FTIR (Fourier‐transform infrared (FTIR)) spectroscopy. The optical properties of the samples were examined by means of UV–Vis and photoluminescence (PL) spectroscopy. It was found that CdS QDs emit a broad band white luminescence between 400 to 700 nm with a peak located at about 510 nm. CdSe QDs emission contained a broad band resulting from trap states between 450 to 800 nm with a peak located at 600 nm. After CdS shell growth, trap states emission was considerably quenched and a near band edge emission was appeared about 480 nm. Optical studies revealed that the core–shell QDs possess strong ultraviolet (UV) ? visible light photocatalytic activity. CdSe/CdS core–shell QDs, showed an enhancement in photodegradation of Methyl orange (MO) compared with CdSe QDs.     

Boosting Photoelectrochemical Water Oxidation of Hematite in Acidic Electrolytes by Surface State Modification

State‐of‐the‐art water‐oxidation catalysts (WOCs) in acidic electrolytes usually contain expensive noble metals such as ruthenium and iridium. However, they too expensive to be implemented broadly in semiconductor photoanodes for photoelectrochemical (PEC) water splitting devices. Here, an Earth‐abundant CoFe Prussian blue analogue (CoFe‐PBA) is incorporated with core–shell Fe₂O₃/Fe₂TiO₅ type II heterojunction nanowires as composite photoanodes for PEC water splitting. Those deliver a high photocurrent of 1.25 mA cm^?2 at 1.23 V versus reversible reference electrode in acidic electrolytes (pH = 1). The enhancement arises from the synergic behavior between the successive decoration of the hematite surface with nanolayers of Fe₂TiO₅ and then, CoFe‐PBA. The underlying physical mechanism of performance enhancement through formation of the Fe₂O₃/Fe₂TiO₅/CoFe‐PBA heterostructure reveals that the surface states’ electronic levels of hematite are modified such that an interfacial charge transfer becomes kinetically favorable. These findings open new pathways for the future design of cheap and efficient hematite‐based photoanodes in acidic electrolytes.     

Harvesting Solar Energy by Means of Charge-Separating Nanocrystals and Their Solids

Conjoining different semiconductor materials in a single nano-composite provides synthetic means for the development of novel optoelectronic materials offering a superior control over the spatial distribution of charge carriers across material interfaces. As this study demonstrates, a combination of donor-acceptor nanocrystal (NC) domains in a single nanoparticle can lead to the realization of efficient photocatalytic^1-5 materials, while a layered assembly of donor- and acceptor-like nanocrystals films gives rise to photovoltaic materials.Initially the paper focuses on the synthesis of composite inorganic nanocrystals, comprising linearly stacked ZnSe, CdS, and Pt domains, which jointly promote photoinduced charge separation. These structures are used in aqueous solutions for the photocatalysis of water under solar radiation, resulting in the production of H₂ gas. To enhance the photoinduced separation of charges, a nanorod morphology with a linear gradient originating from an intrinsic electric field is used⁵. The inter-domain energetics are then optimized to drive photogenerated electrons toward the Pt catalytic site while expelling the holes to the surface of ZnSe domains for sacrificial regeneration (via methanol). Here we show that the only efficient way to produce hydrogen is to use electron-donating ligands to passivate the surface states by tuning the energy level alignment at the semiconductor-ligand interface. Stable and efficient reduction of water is allowed by these ligands due to the fact that they fill vacancies in the valence band of the semiconductor domain, preventing energetic holes from degrading it. Specifically, we show that the energy of the hole is transferred to the ligand moiety, leaving the semiconductor domain functional. This enables us to return the entire nanocrystal-ligand system to a functional state, when the ligands are degraded, by simply adding fresh ligands to the system⁴.To promote a photovoltaic charge separation, we use a composite two-layer solid of PbS and TiO₂ films. In this configuration, photoinduced electrons are injected into TiO₂ and are subsequently picked up by an FTO electrode, while holes are channeled to a Au electrode via PbS layer⁶. To develop the latter we introduce a Semiconductor Matrix Encapsulated Nanocrystal Arrays (SMENA) strategy, which allows bonding PbS NCs into the surrounding matrix of CdS semiconductor. As a result, fabricated solids exhibit excellent thermal stability, attributed to the heteroepitaxial structure of nanocrystal-matrix interfaces, and show compelling light-harvesting performance in prototype solar cells⁷.