Semiconductor‐Based Photoelectrochemical Water Splitting at the Limit of Very Wide Depletion Region

In semiconductor‐based photoelectrochemical (PEC) water splitting, carrier separation and delivery largely relies on the depletion region formed at the semiconductor/water interface. As a Schottky junction device, the trade‐off between photon collection and minority carrier delivery remains a persistent obstacle for maximizing the performance of a water splitting photoelectrode. Here, it is demonstrated that the PEC water splitting efficiency for an n‐SrTiO₃ (n‐STO) photoanode is improved very significantly despite its weak indirect band gap optical absorption (α < 10⁴ cm^?1), by widening the depletion region through engineering its doping density and profile. Graded doped n‐SrTiO₃ photoanodes are fabricated with their bulk heavily doped with oxygen vacancies but their surface lightly doped over a tunable depth of a few hundred nanometers, through a simple low temperature reoxidation technique. The graded doping profile widens the depletion region to over 500 nm, thus leading to very efficient charge carrier separation and high quantum efficiency (>70%) for the weak indirect transition. This simultaneous optimization of the light absorption, minority carrier (hole) delivery, and majority carrier (electron) transport by means of a graded doping architecture may be useful for other indirect band gap photocatalysts that suffer from a similar problem of weak optical absorption.     

Solar Water Splitting by TiO2/CdS/Co–Pi Nanowire Array Photoanode Enhanced with Co–Pi as Hole Transfer Relay and CdS as Light Absorber

The cobalt phosphate water oxidation catalyst (Co–Pi WOC) stabilized, CdS sensitized TiO₂ nanowire arrays for nonsacrificial solar water splitting are reported. In this TiO₂/CdS/Co–Pi photoanode, the Co–Pi WOC acts as hole transfer relay to accelerate the surface water oxidation reaction, CdS serves as light absorber for wider solar spectra harvesting, and TiO₂ matrix provides direct pathway for electron transport. This triple TiO₂/CdS/Co–Pi hybrid photoanode exhibits much enhanced photocurrent density and negatively shifts in onset potential, resulting in 1.5 and 3.4 times improved photoconversion efficiency compared to the TiO₂/CdS and TiO₂ photoanode, respectively. More importantly, the TiO₂/CdS/Co–Pi shows significantly improved photoelectrochemical stability compared to the TiO₂/CdS electrode, with ≈72% of the initial photocurrent retained after 2 h irradiation. The reason for the promoted performance is discussed in detail based on electrochemical measurements. This work provides a new paradigm for designing 1D nanoframework/light absorber/WOC photoanode to simultaneously enhance light absorption, charge separation, and transport and surface water oxidation reaction for efficient and stable solar fuel production.     

Engineering an Earth‐Abundant Element‐Based Bifunctional Electrocatalyst for Highly Efficient and Durable Overall Water Splitting

The simultaneous and efficient evolution of hydrogen and oxygen with earth‐abundant, highly active, and robust bifunctional electrocatalysts is a significant concern in water splitting. Herein, non‐noble metal‐based Ni–Co–S bifunctional catalysts with tunable stoichiometry and morphology are realized. The engineering of electronic structure and subsequent morphological design synergistically contributes to significantly elevated electrocatalytic performance. Stable overpotentials (η₁₀) of 243 mV (vs reversible hydrogen electrode) for oxygen evolution reaction (OER) and 80 mV for hydrogen evolution reaction (HER), as well as Tafel slopes of 54.9 mV dec^?1 for OER and 58.5 mV dec^?1 for HER, are demonstrated. In addition, density functional theory calculations are performed to determine the optimal electronic structure via the electron density differences to verify the enhanced OER activity is related to the Co top site on the (110) surface. Moreover, the tandem bifunctional NiCo₂S₄ exhibit a required voltage of 1.58 V (J = 10 mA cm^?2) for simultaneous OER and HER, and no obvious performance decay is observed after 72 h. When integrated with a GaAs solar cell, the resulting photoassisted water splitting electrolyzer shows a certified solar‐to‐hydrogen efficiency of up to 18.01%, further demonstrating the feasibility of engineering protocols and the promising potential of bifunctional NiCo₂S₄ for large‐scale overall water splitting.     

Iron‐Doped Cobalt Monophosphide Nanosheet/Carbon Nanotube Hybrids as Active and Stable Electrocatalysts for Water Splitting

Developing earth‐abundant, active, and stable electrocatalysts for water splitting is a vital but challenging step for realizing efficient conversion and storage of sustainable energy. Here, a multiscale structure‐engineering approach to construct iron (Fe) doped cobalt monophosphide (CoP) hybrids for efficient electrocatalysis of water splitting is reported. A two‐step method is developed to synthesize CoP nanosheets with uniform Fe doping and hybridization with carbon nanotubes (CNTs). The nanostructuring, uniform doping, and hybridization with CNT afford efficient electrocatalysts comparable to Pt/C for hydrogen evolution reactions in acidic, neutral, and alkaline electrolytes. It is found that the Fe doping level has different effects on catalytic activities in different electrolytes. Furthermore, after in situ oxidization/hydrolysis of the phosphides to corresponding oxyhydroxides, the hybrid electrocatalysts exhibit better performances than the benchmark commercial Ir/C for catalyzing the oxygen evolution reaction. A two‐electrode alkaline water electrolyzer constructed with these hybrid electrocatalysts can afford a current density of 10 mA cm^?2 at a voltage of 1.5 V.     

Interface Engineering for Modulation of Charge Carrier Behavior in ZnO Photoelectrochemical Water Splitting

Photoelectrochemical water splitting via consumption of solar energy is considered an alternative approach to address both fossil resource and global warming issues. On the basis of the bottom‐up technique, major strategies have been developed to enrich the complexity of nanostructures by incorporating various functional components to realize outstanding photoelectrochemical (PEC) performance for hydrogen evolution, such as high solar‐to‐hydrogen efficiency and long‐term stability. In such a PEC system, each nanomaterial component individually, and more importantly, together with the formed interfaces, contributes to PEC performance elevation. Specifically, the two types of interfaces that have emerged, i.e., the interfaces between photoelectrodes and electrolytes (solid–liquid contact) and the interfaces inside photoelectrodes (solid–solid contact), have both been effectively engineered to facilitate charge separation and transportation and even enhance the antiphotocorrosion properties. A comprehensive understanding, summary, and review of such interface engineering protocols may provide novel and effective approaches for PEC system designing.     

Metal–Organic Framework Derived Co3O4/TiO2/Si Heterostructured Nanorod Array Photoanodes for Efficient Photoelectrochemical Water Oxidation

A novel hierarchical structured photoanode based on metal–organic frameworks (MOFs)‐derived porous Co₃O₄‐modified TiO₂ nanorod array grown on Si (MOFs‐derived Co₃O₄/TiO₂/Si) is developed as photoanode for efficiently photoelectrochemical (PEC) water oxidation. The ternary Co₃O₄/TiO₂/Si heterojunction displays enhanced carrier separation performance and electron injection efficiency. In the ternary system, an abnormal type‐II heterojunction between TiO₂ and Si is introduced, because the conduction band and valence band position of Si are higher than those of TiO₂, the photogenerated electrons from TiO₂ will rapidly recombine with the photogenerated holes from Si, thus leading to an efficient separation of photogenerated electrons from Si/holes from TiO₂ at the TiO₂/Si interface, greatly improving the separation efficiency of photogenerated hole within TiO₂ and enhances the photogenerated electron injection efficiency in Si. While the MOFs‐derived Co₃O₄ obviously improves the optical‐response performance and surface water oxidation kinetics due to the large specific surface area and porous channel structure. Compared with MOFs‐derived Co₃O₄/TiO₂/FTO photoanode, the synergistic function in the MOFs‐derived Co₃O₄/TiO₂/Si NR photoanode brings greatly enhanced photoconversion efficiency of 0.54% (1.04 V vs reversible hydrogen electrode) and photocurrent density of 2.71 mA cm^?2 in alkaline electrolyte. This work provides promising methods for constructing high‐performance PEC water splitting photoanode based on MOFs‐derived materials.     

3D Self‐Supported Fe‐Doped Ni2P Nanosheet Arrays as Bifunctional Catalysts for Overall Water Splitting

The development of highly efficient bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial for improving the efficiency of overall water splitting, but still remains challenging issue. Herein, 3D self‐supported Fe‐doped Ni₂P nanosheet arrays are synthesized on Ni foam by hydrothermal method followed by in situ phosphorization, which serve as bifunctional electrocatalysts for overall water splitting. The as‐synthesized (Ni_0.33Fe_0.67)₂P with moderate Fe doping shows an outstanding OER performance, which only requires an overpotential of ≈230 mV to reach 50 mA cm^?2 and is more efficient than the other Fe incorporated Ni₂P electrodes. In addition, the (Ni_0.33Fe_0.67)₂P exhibits excellent activity toward HER with a small overpotential of ≈214 mV to reach 50 mA cm^?2. Furthermore, an alkaline electrolyzer is measured using (Ni_0.33Fe_0.67)₂P electrodes as cathode and anode, respectively, which requires cell voltage of 1.49 V to reach 10 mA cm^?2 as well as shows excellent stability with good nanoarray construction. Such good performance is attributed to the high intrinsic activity and superaerophobic surface property.     

Efficient and Durable 3D Self‐Supported Nitrogen‐Doped Carbon‐Coupled Nickel/Cobalt Phosphide Electrodes: Stoichiometric Ratio Regulated Phase‐ and Morphology‐Dependent Overall Water Splitting Performance

The construction of a novel 3D self‐supported integrated Ni_xCo_2?xP@NC (0 < x < 2) nanowall array (NA) on Ni foam (NF) electrode constituting highly dispersed Ni_xCo_2?xP nanoparticles, nanorods, nanocapsules, and nanodendrites embedded in N‐doped carbon (NC) NA grown on NF is reported. Benefiting from the collective effects of special morphological and structural design and electronic structure engineering, the Ni_xCo_2?xP@NC NA/NF electrodes exhibit superior electrocatalytic performance for water splitting with an excellent stability in a wide pH range. The optimal NiCoP@NC NA/NF electrode exhibits the best hydrogen evolution reaction (HER) activity in acidic solution so far, attaining a current density of 10 mA cm^?2 at an overpotential of 34 mV. Moreover, the electrode manifests remarkable performances toward both HER and oxygen evolution reaction in alkaline medium with only small overpotentials of 37 mV at 10 mA cm^?2 and 305 mV at 50 mA cm^?2, respectively. Most importantly, when coupling with the NiCoP@NC NA/NF electrode for overall water splitting, an alkali electrolyzer delivers a current density of 20 mA cm^?2 at a very low cell voltage of ≈1.56 V. In addition, the NiCoP@NC NA/NF electrode has outstanding long‐term durability at j = 10 mA cm^?2 with a negligible degradation in current density over 22 h in both acidic and alkaline media.     

Large‐Size,Porous, Ultrathin NiCoP Nanosheets for Efficient Electro/Photocatalytic Water Splitting

Porous ultrathin 2D catalysts are attracting great attention in the field of electro/photocatalytic hydrogen evolution reaction (HER) and overall water splitting. Herein, a universal pH‐controlled wet‐chemical strategy is reported followed by thermal and phosphorization treatment to prepare large‐size, porous and ultrathin bimetallic phosphide (NiCoP) nanosheets, in which graphene oxide is adopted as a template to determine the size of products. The thickness of the resultant NiCoP nanosheets ranges from 3.5 to 12.8 nm via delicately adjusting pH from 7.8 to 8.5. The thickness‐dependent electrocatalytic performance is evidenced experimentally and explained by computational studies. The prepared large‐size ultrathin NiCoP nanosheets show excellent bifunctional electrocatalytic activity for overall water splitting, with low overpotentials of 34.3 mV for HER and 245.0 mV for oxygen evolution reaction, respectively, at 10 mA cm^?2. Furthermore, the NiCoP nanosheets exhibit superior photocatalytic HER performance, achieving a high HER rate of 238.2 mmol h^?1 g^?1 in combination with commonly used photocatalyst CdS, which is far superior to that of Pt/CdS (81.7 mmol h^?1 g^?1). All these results demonstrate large‐size porous ultrathin NiCoP nanosheets as an efficient and multifunctional electro/photocatalyst for water splitting.     

Heterogeneous Bimetallic Mo-NiPx/NiSy as a Highly Efficient Electrocatalyst for Robust Overall Water Splitting

Highly efficient electrocatalysts composed of earth-abundant elements are desired for water-splitting to produce clean and renewable chemical fuel. Herein, a heteroatomic-doped multi-phase Mo-doped nickel phosphide/nickel sulfide (Mo-NiP_x/NiS_y) nanowire electrocatalyst is designed by a successive phosphorization and sulfuration method for boosting overall water splitting (both oxygen and hydrogen evolution reactions (HER)) in alkaline solution. As expected, the Mo-NiP_x/NiS_y electrode possesses low overpotentials both at low and high current densities in HER, while the Mo-NiP_x/NiS_y heterostructure exhibits high active performance with ultra-low overpotentials of 137, 182, and 250 mV at the current density of 10, 100, and 400 mA cm⁻² in 1 m KOH solution, respectively, in oxygen evolution reaction. In particular, the as-prepared Mo-NiP_x/NiS_y electrodes exhibit remarkable full water splitting performance at both low and high current densities of 10, 100, and 400 mA cm⁻² with 1.42, 1.70, and 2.36 V, respectively, which is comparable to commercial electrolysis.     

Mo-/Co-N-C Hybrid Nanosheets Oriented on Hierarchical Nanoporous Cu as Versatile Electrocatalysts for Efficient Water Splitting

Designing robust and cost-effective electrocatalysts based on Earth-abundant elements is crucial for large-scale hydrogen production through electrochemical water splitting. Here, nitrogen-doped carbon engrafted Mo₂N/CoN hybrid nanosheets that are seamlessly oriented on hierarchical nanoporous Cu scaffold (Mo-/Co-N-C/Cu), as highly efficient electrocatalysts for alkaline hydrogen evolution reaction are reported. The constituent heterostructured Mo₂N/CoN nanosheets work as bifunctional electroactive sites for both water dissociation and adsorption/desorption of hydrogen intermediates while the nitrogen-doped carbon bridges electron transfers between electroactive sites and interconnective Cu current collectors by making use of Mo-/Co-N-C bonds and intimate C/Cu contacts at interfaces. As a consequence of unique architecture having electroactive sites to be sufficiently accessible, self-supported nanoporous Mo-/Co-N-C/Cu hybrid electrodes exhibit outstanding electrocatalysis in 1 m KOH, with a negligible onset overpotential and a low Tafel slope of 47 mV dec⁻¹. They only take overpotential of as low as 230 mV to reach current density of 1000 mA cm⁻². When coupled with their electro-oxidized derivatives that mediate efficiently the oxygen evolution reaction, the alkaline water electrolyzer can achieve ≈100 mA cm⁻² at 1.622 V in 1 m KOH electrolyte, ≈0.343 V lower than the device constructed with commercially available Pt/C and Ir/C nanocatalysts immobilized on nanoporous Cu electrodes.     

Kinetically Controlled Coprecipitation for General Fast Synthesis of Sandwiched Metal Hydroxide Nanosheets/Graphene Composites toward Efficient Water Splitting

The development of cost‐effective and applicable strategies for producing efficient oxygen evolution reaction (OER) electrocatalysts is crucial to advance electrochemical water splitting. Herein, a kinetically controlled room‐temperature coprecipitation is developed as a general strategy to produce a variety of sandwich‐type metal hydroxide/graphene composites. Specifically, well‐defined α‐phase nickel cobalt hydroxide nanosheets are vertically assembled on the entire graphene surface (NiCo‐HS@G) to provide plenty of accessible active sites and enable facile gas escaping. The tight contact between NiCo‐HS and graphene promises effective electron transfer and remarkable durability. It is discovered that Ni doping adjusts the nanosheet morphology to augment active sites and effectively modulates the electronic structure of Co center to favor the adsorption of oxygen species. Consequently, NiCo‐HS@G exhibits superior electrocatalytic activity and durability for OER with a very low overpotential of 259 mV at 10 mA cm^?2. Furthermore, a practical water electrolyzer demonstrates a small cell voltage of 1.51 V to stably achieve the current density of 10 mA cm^?2, and 1.68 V to 50 mA cm^?2. Such superior electrocatalytic performance indicates that this facile and manageable strategy with low energy consumption may open up opportunities for the cost‐effective mass production of various metal hydroxides/graphene nanocomposites with desirable morphology and competing performance for diverse applications.     

Highly Efficient Photoelectrochemical Water Splitting: Surface Modification of Cobalt‐Phosphate‐Loaded Co3O4/Fe2O3 p–n Heterojunction Nanorod Arrays

Hematite (α‐Fe₂O₃) as a photoanode material for photoelectrochemical (PEC) water splitting suffers from the two problems of poor charge separation and slow water oxidation kinetics. The construction of p–n junction nanostructures by coupling of highly stable Co₃O₄ in aqueous alkaline environment to Fe₂O₃ nanorod arrays with delicate energy band positions may be a challenging strategy for efficient PEC water oxidation. It is demonstrated that the designed p‐Co₃O₄/n‐Fe₂O₃ junction exhibits superior photocurrent density, fast water oxidation kinetics, and remarkable charge injection and bulk separation efficiency (η_inj and η_sep), attributing to the high catalytic behavior of Co₃O₄ for the oxygen evolution reaction as well as the induced interfacial electric field that facilitates separation and transportation of charge carriers. In addition, a cocatalyst of cobalt phosphate (Co‐Pi) is introduced, which brings the PEC performance to a high level. The resultant Co‐Pi/Co₃O₄/Ti:Fe₂O₃ photoanode shows a photocurrent density of 2.7 mA cm^?2 at 1.23 V_RHE (V vs reversible hydrogen electrode), 125% higher than that of the Ti:Fe₂O₃ photoanode. The optimized η_inj and η_sep of 91.6 and 23.0% at 1.23 V_RHE are achieved on Co‐Pi/Co₃O₄/Ti:Fe₂O₃, respectively, corresponding to the 70 and 43% improvements compared with those of Ti:Fe₂O₃. Furthermore, Co‐Pi/Co₃O₄/Ti:Fe₂O₃ shows a low onset potential of 0.64 V_RHE and long‐time PEC stability.     

Dual‐Phase Engineering of Nickel Boride‐Hydroxide Nanoparticles toward High‐Performance Water Oxidation Electrocatalysts

The development of earth‐abundant and efficient oxygen evolution reaction (OER) electrocatalysts is necessary for green hydrogen production. The preparation of efficient OER electrocatalysts requires both the adsorption sites and charge transfer on the catalyst surface to be suitably engineered. Herein, the design of an electrocatalyst is reported with significantly enhanced water oxidation performance via dual‐phase engineering, which displays a high number of adsorption sites and facile charge transfer. More importantly, a simple chemical etching process enables the formation of a highly metallic transition boride phase in conjunction with the transition metal hydroxide phase with abundant adsorption sites available for the intermediates formed in the OER. In addition, computational simulations are carried out to demonstrate the water oxidation mechanism and the real active sites in this engineered material. This research provides a new material design strategy for the preparation of high‐performance OER electrocatalysts.     

Novel Iron/Cobalt‐Containing Polypyrrole Hydrogel‐Derived Trifunctional Electrocatalyst for Self‐Powered Overall Water Splitting

Development of efficient, low‐cost, and durable electrocatalysts for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) is of significant importance for many electrochemical devices, such as rechargeable metal–air batteries, fuel cells, and water electrolyzers. Here, a novel approach for the synthesis of a trifunctional electrocatalyst derived from iron/cobalt‐containing polypyrrole (PPy) hydrogel is reported. This strategy relies on the formation of a supramolecularly cross‐linked PPy hydrogel that allows for efficient and homogeneous incorporation of highly active Fe/Co–N–C species. Meanwhile, Co nanoparticles are also formed and embedded into the carbon scaffold during the pyrolysis process, further promoting electrochemical activities. The resultant electrocatalyst exhibits prominent catalytic activities for ORR, OER, and HER, surpassing previously reported trifunctional electrocatalysts. Finally, it is demonstrated that the as‐obtained trifunctional electrocatalyst can be used for electrocatalytic overall water splitting in a self‐powered manner under ambient conditions. This work offers new prospects in developing highly active, nonprecious‐metal‐based electrocatalysts in electrochemical energy devices.     

Interlayer Band‐to‐Band Tunneling and Negative Differential Resistance in van der Waals BP/InSe Field‐Effect Transistors

Atomically thin layers of van der Waals (vdW) crystals offer an ideal material platform to realize tunnel field‐effect transistors (TFETs) that exploit the tunneling of charge carriers across the forbidden gap of a vdW heterojunction. This type of device requires a precise energy band alignment of the different layers of the junction to optimize the tunnel current. Among 2D vdW materials, black phosphorus (BP) and indium selenide (InSe) have a Brillouin zone‐centered conduction and valence bands, and a type II band offset, both ideally suited for band‐to‐band tunneling. TFETs based on BP/InSe heterojunctions with diverse electrical transport characteristics are demonstrated: forward rectifying, Zener tunneling, and backward rectifying characteristics are realized in BP/InSe junctions with different thickness of the BP layer or by electrostatic gating of the junction. Electrostatic gating yields a large on/off current ratio of up to 10⁸ and negative differential resistance at low applied voltages (V ≈ 0.2 V). These findings illustrate versatile functionalities of TFETs based on BP and InSe, offering opportunities for applications of these 2D materials beyond the device architectures reported in the current literature.     

Ternary Metal Phosphide with Triple‐Layered Structure as a Low‐Cost and Efficient Electrocatalyst for Bifunctional Water Splitting

Development of low‐cost, high‐performance, and bifunctional electrocatalysts for water splitting is essential for renewable and clean energy technologies. Although binary phosphides are inexpensive, their performance is not as good as noble metals. Adding a third metal element to binary phosphides (Ni‐P, Co‐P) provides the opportunity to tune their crystalline and electronic structures and thus their electrocatalytic properties. Here, ternary phosphide (NiCoP) films with different nickel to cobalt ratios via an electrodeposition technique are synthesized. The films have a triple‐layered and hierarchical morphology, consisting of nanosheets in the bottom layer, ≈90–120 nm nanospheres in the middle layer, and larger spherical particles on the top layer. The ternary phosphides exhibit versatile activities that are strongly dependent on the Ni/Co ratios and Ni_0.51Co_0.49P film is found to have the best electrocatalytic activities for both hydrogen evolution reactions and oxygen evolution reactions. The high performance of the ternary phosphide film is attributed to enhanced electric conductivity so that reaction kinetics is accelerated, enlarged surface area due to the hierarchical and three‐layered morphology, and increased local electric dipole so that the energy barrier for the water splitting reaction is lowered.     

An Advanced Nitrogen‐Doped Graphene/Cobalt‐Embedded Porous Carbon Polyhedron Hybrid for Efficient Catalysis of Oxygen Reduction and Water Splitting

A novel hybrid electrocatalyst consisting of nitrogen‐doped graphene/cobalt‐embedded porous carbon polyhedron (N/Co‐doped PCP//NRGO) is prepared through simple pyrolysis of graphene oxide‐supported cobalt‐based zeolitic imidazolate‐frameworks. Remarkable features of the porous carbon structure, N/Co‐doping effect, introduction of NRGO, and good contact between N/Co‐doped PCP and NRGO result in a high catalytic efficiency. The hybrid shows excellent electrocatalytic activities and kinetics for oxygen reduction reaction in basic media, which compares favorably with those of the Pt/C catalyst, together with superior durability, a four‐electron pathway, and excellent methanol tolerance. The hybrid also exhibits superior performance for hydrogen evolution reaction, offering a low onset overpotential of 58 mV and a stable current density of 10 mA cm^?2 at 229 mV in acid media, as well as good catalytic performance for oxygen evolution reaction (a small overpotential of 1.66 V for 10 mA cm^?2 current density). The dual‐active‐site mechanism originating from synergic effects between N/Co‐doped PCP and NRGO is responsible for the excellent performance of the hybrid. This development offers an attractive catalyst material for large‐scale fuel cells and water splitting technologies.