Fullerene as a Photoelectron Transfer Promoter Enabling Stable TiO2‐Protected Sb2Se3 Photocathodes for Photo‐Electrochemical Water Splitting

Understanding the degradation mechanisms of photoelectrodes and improving their stability are essential for fully realizing solar‐to‐hydrogen conversion via photo‐electrochemical (PEC) devices. Although amorphous TiO₂ layers have been widely employed as a protective layer on top of p‐type semiconductors to implement durable photocathodes, gradual photocurrent degradation is still unavoidable. This study elucidates the photocurrent degradation mechanisms of TiO₂‐protected Sb₂Se₃ photocathodes and proposes a novel interface‐modification methodology in which fullerene (C₆₀) is introduced as a photoelectron transfer promoter for significantly enhancing long‐term stability. It is demonstrated that the accumulation of photogenerated electrons at the surface of the TiO₂ layer induces the reductive dissolution of TiO₂, accompanied by photocurrent degradation. In addition, the insertion of the C₆₀ photoelectron transfer promoter at the Pt/TiO₂ interface facilitates the rapid transfer of photogenerated electrons out of the TiO₂ layer, thereby yielding enhanced stability. The Pt/C₆₀/TiO₂/Sb₂Se₃ device exhibits a high photocurrent density of 17 mA cm^?2 and outstanding stability over 10 h of operation, representing the best PEC performance and long‐term stability compared with previously reported Sb₂Se₃‐based photocathodes. This research not only provides in‐depth understanding of the degradation mechanisms of TiO₂‐protected photocathodes, but also suggests a new direction to achieve durable photocathodes for photo‐electrochemical water splitting.     

Recent Advances and Emerging Trends in Photo‐Electrochemical Solar Energy Conversion

Photo‐electrochemical (PEC) solar energy conversion offers the promise of low‐cost renewable fuel generation from abundant sunlight and water. In this Review, recent developments in photo‐electrochemical water splitting are discussed with respect to this promise. State‐of‐the‐art photo‐electrochemical device performance is put in context with the current understanding of the necessary requirements for cost‐effective solar hydrogen generation (in terms of solar‐to‐hydrogen conversion efficiency and system durability, in particular). Several important studies of photo‐electrochemical hydrogen generation at p‐type photocathodes are highlighted, mostly with protection layers (for enhanced durability), but also a few recent examples where protective layers are not needed. Recent work with the widely studied n‐type BiVO₄ photoanode is detailed, which highlights the needs and necessities for the next big photoanode material yet to be discovered. The emerging new research direction of photo‐electrocatalytic upgrading of biomass substrates toward value‐added chemicals is then discussed, before closing with a commentary on how research on PEC materials remains a worthwhile endeavor.     

3D Porous Pyramid Heterostructure Array Realizing Efficient Photo‐Electrochemical Performance

Direct photo‐electrochemical (PEC) water splitting is of great practical interest for developing a sustainable energy systems, but remains a big challenge owing to sluggish charge separation, low efficiency, and poor stability. Herein, a 3D porous In₂O₃/In₂S₃ pyramid heterostructure array on a fluorine‐doped tin oxide substrate is fabricated by an ion exchange–induced synthesis strategy. Based on the synergistic structural and electronic modulations from density functional theory calculations and experimental observations, 3D porous In₂O₃/In₂S₃ photoanode by the protective layer delivers a low onset potential of ≈0.02 V versus reversible hydrogen electrode (RHE), the highest photocurrent density of 8.2 mA cm^?2 at 1.23 V versus RHE among all the In₂S₃ photoanodes reported to date, an incident photon‐to‐current efficiency of 76% at 400 nm, and high stability over 20 h for PEC water splitting are reported. This work provides an alternative promising prototype for the design and construction of novel heterostructures in robust PEC water splitting applications.     

3D‐Branched ZnO/CdS Nanowire Arrays for Solar Water Splitting and the Service Safety Research

Modulation of broadband light trapping through assembly of 3D structures and modification with narrow band‐gap semiconductors provide an effective way to improve the photoelectrochemical (PEC) performance. Here, 3D‐branched ZnO nanowire arrays (NWAs) modified with cadmium sulfide (CdS) nanoparticles are designed and synthesized via solution chemical routes. The 3D‐branched ZnO NWA–CdS nanoparticle photoanodes show an excellent PEC performance in UV and visible region and the maximum photo‐to‐hydrogen conversion efficiency reaches to 3.1%. The high performance of 3D‐branched ZnO NWA–CdS composites is mainly attributed to the excellent carrier collection capability and high light‐trapping ability of 3D‐branched ZnO NWAs as well as the excellent photocatalytic activity of CdS nanoparticles in the visible region. In addition, the photocorrosion mechanism of 3D‐branched ZnO NWA–CdS photoanodes is systematically investigated, and a protective TiO₂ layer is deposited onto the photoanodes to elevate the PEC stability. The results benefit a deeper understanding of the role of 3D‐branched structures decorated with narrow band‐gap semiconductors in solar water splitting.     

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.     

Interfacial Modification Using Hydrogenated TiO2 Electron‐Selective Layers for High‐Efficiency and Light‐Soaking‐Free Organic Solar Cells

Optimizing the interfacial contacts between the photoactive layer and the electrodes is an important factor in determining the performance of organic solar cells (OSCs). A charge‐selective layer with tailored electrical properties enhances the charge collection efficiency and interfacial stability. Here, the potential of hydrogenated TiO₂ nanoparticles (H‐TiO₂ NPs) as an efficient electron‐selective layer (ESL) material in OSCs is reported for the first time. The H‐TiO₂ is synthesized by discharge plasma in liquid at atmospheric pressure, which has the benefits of a simple one‐pot synthesis process, rapid and mild reaction conditions, and the capacity for mass production. The H‐TiO₂ exhibits high conductivity and favorable energy level formation for efficient electron extraction, providing a basis for an efficient bilayer ESL system composed of conjugated polyelectrolyte/H‐TiO₂. Thus, the enhanced charge transport and extraction efficiency with reduced recombination losses at the cathode interfacial contacts is achieved. Moreover, the OSCs composed of H‐TiO₂ are almost free of light soaking, which has been reported to severely limit the performance and stability of OSCs based on conventional TiO₂ ESLs. Therefore, H‐TiO₂ as a new efficient, stable, and cost‐effective ESL material has the potential to open new opportunities for optoelectronic devices.     

Carbon Nitride/Reduced Graphene Oxide Film with Enhanced Electron Diffusion Length: An Efficient Photo‐Electrochemical Cell for Hydrogen Generation

Polymeric carbon nitride (CN) has emerged as a promising semiconductor for energy‐related applications. However, its utilization in photo‐electrochemical cells is still very limited owing to poor electron–hole separation efficiency, short electron diffusion length, and low absorption coefficient. Here the synthesis of a highly porous carbon nitride/reduced graphene oxide (CN‐rGO) film with good photo‐electrochemical properties is reported. The CN‐rGO film exhibits long electron diffusion length and high electrochemical active surface area, good charge separation, and enhanced light‐harvesting properties. The film displays a 20‐fold enhancement of photocurrent density over pristine CN, reaching up to 75 µA cm^?2 at 1.23 V versus reversible hydrogen electrode (RHE) in an alkaline solution, as well as stability over a wide pH range. Photocurrent measurements with a hole scavenger reveal a photocurrent density of 660 µA cm^?2 at 1.23 V versus RHE and a quantum efficiency of 60% at 400 nm, resulting in the production of 0.8 mol h^?1 g^?1 of hydrogen. The substantial photo‐electrochemical activity enhancement and hydrogen production together with the low price, high electrochemical surface area, long electron diffusion length, stability under harsh condition, and tunable photophysical properties of CN materials open many possibilities for their utilization in (photo)electrochemical and electronic devices.     

MoS2‐Based All‐Purpose Fibrous Electrode and Self‐Powering Energy Fiber for Efficient Energy Harvesting and Storage

Here an all‐purpose fibrous electrode based on MoS₂ is demonstrated, which can be employed for versatile energy harvesting and storage applications. In this coaxial electrode, ultrathin MoS₂ nanofilms are grown on TiO₂ nanoparticles coated carbon fiber. The high electrochemical activity of MoS₂ and good conductivity of carbon fiber synergistically lead to the remarkable performances of this novel composite electrode in fibrous dye‐sensitized solar cells (showing a record‐breaking conversion efficiency of 9.5%) and high‐capacity fibrous supercapacitors. Furthermore, a self‐powering energy fiber is fabricated by combining a fibrous dye‐sensitized solar cell and a fibrous supercapacitor into a single device, showing very fast charging capability (charging in 7 s under AM1.5G solar illumination) and an overall photochemical‐electricity energy conversion efficiency as high as 1.8%. In addition, this wire‐shaped electrode can also be used for fibrous Li‐ion batteries and electrocatalytic hydrogen evolution reactions. These applications indicate that the MoS₂‐based all‐purpose fibrous electrode has great potential for the construction of high‐performance flexible and wearable energy devices.     

MOF‐Based Transparent Passivation Layer Modified ZnO Nanorod Arrays for Enhanced Photo‐Electrochemical Water Splitting

This study introduces zeolitic imidazolate framework‐8 (ZIF‐8) as the first metal‐organic framework based transparent surface passivation layer for photo‐electrochemical (PEC) water splitting. A significant enhancement for PEC water oxidation is demonstrated based on the in situ seamless coating of ZIF‐8 surface passivation layer on Ni foam (NF) supported ZnO nanorod arrays photoanode. The PEC performance is improved by optimizing the ZIF‐8 thickness and by grafting Ni(OH)₂ nanosheets as synergetic co‐catalyst. With respect to ZnO/NF, the optimized Ni(OH)₂/ZIF‐8/ZnO/NF photoanode exhibits a two times larger photocurrent density of 1.95 mA cm^?2 and also a two times larger incident photon to current conversion efficiency of 40.05% (350 nm) at 1.23 V versus RHE (V_RHE) under AM 1.5 G. The synergetic surface passivation and the co‐catalyst modification contribute to prolonging the charge lifetime, to promoting the charge transfer, and to decreasing the overpotential for water oxidation.     

Light‐Driven BiVO4–C Fuel Cell with Simultaneous Production of H2O2

Photoelectrochemical (PEC) systems have been researched for decades due to their great promise to convert sunlight to fuels. The majority of the research on PEC has been using light to split water to hydrogen and oxygen, and its performance is limited by the need of additional bias. Another research direction on PEC using light, is to decompose organic materials while producing electricity. In this work, the authors report a new type of unassisted PEC system that uses light, water and oxygen to simultaneously produce electricity and hydrogen peroxide (H₂O₂) on both the photoanode and cathode, which is essentially a light‐driven fuel cell with H₂O₂ as the main product at the two electrodes, meanwhile achieving a maximum power density of 0.194 mW cm^‐2, an open circuit voltage of 0.61 V, and a short circuit current density of 1.09 mA cm^‐2. The electricity output can be further used as a sign for cell function when accompanied by a detector such as a light‐emitting diode (LED) light or a multimeter. This is the first work that shows H₂O₂ two‐side generation with a strict key factors study of the system, with a clear demonstration of electricity output ability using low‐cost earth abundant materials on both sides, which represents an exciting new direction for PEC systems.     

Atomic Layer Deposition as a General Method Turns any 3D‐Printed Electrode into a Desired Catalyst: Case Study in Photoelectrochemisty

3D‐printing technologies have begun to revolutionize many manufacturing processes, however, there are still significant limitations that are yet to be overcome. In particular, the material from which the products are fabricated is limited by the 3D‐printing material precursor. Particularly, for photoelectrochemical (PEC) energy applications, the as‐printed electrodes can be used as is, or modified by postfabrication processes, e.g., electrochemical deposition or anodization, to create active layers on the 3D‐printed electrodes. However, the as‐printed electrodes are relatively inert for various PEC energy applications, and the aforementioned postfabrication processing techniques do not offer layer conformity or control at the Ångström/nano level. Herein, for the first time, atomic layer deposition (ALD) is utilized in conjunction with metal 3D‐printing to create active electrodes. To illustrate the proof‐of‐concept, TiO₂ is deposited by ALD onto stainless steel 3D‐printed electrodes and subsequently investigated as a photoanode for PEC water oxidation. Furthermore, by tuning the TiO₂ thickness by ALD, the activity can be optimized. By combining 3D‐printing and ALD, instead of other metal deposition techniques, i.e., sputtering, rapid prototyping of electrodes with controllable thickness of the desired material onto an as‐printed electrodes with any porosity can be achieved that can benefit a multitude of energy applications.     

Dramatically Enhanced Ambient Ammonia Electrosynthesis Performance by In‐Operando Created Li–S Interactions on MoS2 Electrocatalyst

The Haber‐Bosch process can be replaced by the ambient electrocatalytic N₂ reduction reaction (NRR) to produce NH₃ if suitable electrocatalysts can be developed. However, to develop high performance N₂ fixation electrocatalysts, a key issue to be resolved is to achieve efficient hydrogenation of N₂ without interference by the thermodynamically favored hydrogen evolution reaction (HER). Herein, in‐operando created strong Li–S interactions are reported to empower the S‐rich MoS₂ nanosheets with superior NRR catalytic activity and HER suppression ability. The Li⁺ interactions with S‐edge sites of MoS₂ can effectively suppress hydrogen evolution reaction by reducing H* adsorption free energy from 0.03 to 0.47 eV, facilitate N₂ adsorption by increasing N₂ adsorption free energy from –0.32 to –0.70 eV and enhance electrocatalytic N₂ reduction activity by decreasing the activation energy barrier of the reaction control step (*N₂ → *N₂H) from 0.84 to 0.42 eV. A NH₃ yield rate of 43.4 μg h^?1 mg^?1 MoS₂ with a faradaic efficiency (FE) of 9.81% can be achieved in presence of strong Li–S interactions, more than 8 and 18 times by the same electrocatalyst in the absence of Li–S interactions. This report opens a new way to design and develop catalysts and catalysis systems.     

Atomically Thin Mesoporous In2O3–x/In2S3 Lateral Heterostructures Enabling Robust Broadband‐Light Photo‐Electrochemical Water Splitting

Atomically thin 2D heterostructures have opened new realms in electronic and optoelectronic devices. Herein, 2D lateral heterostructures of mesoporous In₂O_3–x/In₂S₃ atomic layers are synthesized through the in situ oxidation of In₂S₃ atomic layers by an oxygen plasma‐induced strategy. Based on experimental observations and theoretical calculations, the prolonged charge carrier lifetime and increased electron density reveal the efficient photoexcited carrier transport and separation in the In₂O_3–x/In₂S₃ layers by interfacial bonding at the atomic level. As expected, the synergistic structural and electronic modulations of the In₂O_3–x/In₂S₃ layers generate a photocurrent of 1.28 mA cm^?2 at 1.23 V versus a reversible hydrogen electrode, nearly 21 and 79 times higher than those of the In₂S₃ atomic layers and bulk counterpart, respectively. Due to the large surface area, abundant active sites, broadband‐light harvesting ability, and effective charge transport pathways, the In₂O_3–x/In₂S₃ layers build efficient pathways for photoexcited charge in the 2D semiconductive channels, expediting charge transport and kinetic processes and enhancing the robust broadband‐light photo‐electrochemical water splitting performance. This work paves new avenues for the exploration and design of atomically thin 2D lateral heterostructures toward robust photo‐electrochemical applications and solar energy utilization.     

Titanium Dioxide Mesoporous Electrodes for Solid‐State Dye‐Sensitized Solar Cells: Cross‐Analysis of the Critical Parameters

We report a comparative study on the use of four different mesoporous titanium dioxide (TiO₂) photo‐electrodes for the fabrication of solid‐state dye‐sensitized solar cells (sDSSCs). The photovoltaic parameters of the device correlate with several intrinsic properties of the film, based not only on its morphological features, as commonly considered in standard characterizations, but also on the transport and the electronic properties of the photo‐electrode. These properties differ significantly for TiO₂ electrodes processed using different colloidal pastes, and are decisive for the photovoltaic efficiency, ranging from 3.7% up to 5.1%. In particular, the dielectric permittivity of each mesoporous layer (ε_eff) and the number of traps (N_t) determined by the space‐charge‐limited current (SCLC) theory are found to be a bottle‐neck for the charge transport, greatly influencing the fill factor (FF) and open circuit voltage (V_oc) of the cells. In addition, a direct correlation between TiO₂ surface potential with the V_oc was established. Cross‐analysis of key macroscopic parameters of the films prior to integration in the devices, in particular focusing on the determination of the capacitance and surface potential shift of the TiO₂ mesoporous anode, represents a straightforward yet powerful method to screen and select the most suitable TiO₂ for applications in sDSSCs.     

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.     

Tailored TiO2 Protection Layer Enabled Efficient and Stable Microdome Structured p‐GaAs Photoelectrochemical Cathodes

Group III–V compound semiconductors are a promising group of materials for photoelectrochemical (PEC) applications. In this work, a metal assisted wet etching approach is adapted to acquiring a large‐area patterned microdome structure on p‐GaAs surface. In addition, atomic layer deposition is used to deposit a TiO₂ protection layer with controlled thickness and crystallinity. Based on a PEC photocathode design, the optimal configuration achieves a photocurrent of ?5 mA cm^?2 under ?0.8 V versus Ag/AgCl in a neutral pH electrolyte. The TiO₂ coating with a particular degree of crystallization deposited via controlled temperature demonstrates a superior stability over amorphous coating, enabling a remarkably stable operation, for as long as 60 h. The enhanced charge separation induced by favorable band alignment between GaAs and TiO₂ contributes simultaneously to the elevated solar conversion efficiency. This approach provides a promising solution to further development of group III–V compounds and other photoelectrodes with high efficiency and excellent durability for solar fuel generation.     

p‐Type CuI Islands on TiO2 Electron Transport Layer for a Highly Efficient Planar‐Perovskite Solar Cell with Negligible Hysteresis

Compact TiO₂ is widely used as an electron transport material in planar‐perovskite solar cells. However, TiO₂‐based planar‐perovskite solar cells exhibit low efficiencies due to intrinsic problems such as the unsuitable conduction band energy and low electron extraction ability of TiO₂. Herein, the planar TiO₂ electron transport layer (ETL) of perovskite solar cells is modified with ionic salt CuI via a simple one‐step spin‐coating process. The p‐type nature of the CuI islands on the TiO₂ surface leads to modification of the TiO₂ band alignment, resulting in barrier‐free contacts and increased open‐circuit voltage. It is found that the polarity of the CuI‐modified TiO₂ surface can pull electrons to the interface between the perovskite and the TiO₂, which improves electron extraction and reduces nonradiative recombination. The CuI solution concentration is varied to control the electron extraction of the modified TiO₂ ETL, and the optimized device shows a high efficiency of 19.0%. In addition, the optimized device shows negligible hysteresis, which is believed to be due to the removal of trap sites and effective electron extraction by CuI‐modified TiO₂. These results demonstrate the hitherto unknown effect of p‐type ionic salts on electron transport material.     

Recent Development of Ni/Fe‐Based Micro/Nanostructures toward Photo/Electrochemical Water Oxidation

The oxygen evolution reaction (OER), as an important process involved in water splitting and rechargeable metal–air batteries, has drawn increasing attention in the context of clean energy generation and efficient energy storage. This review concerns the progress and new discoveries in the field of Ni/Fe‐based micro/nanostructures toward electrochemical and photo‐electrochemical (PEC) water oxidation during last few years. First, toward the design and construction of new electrocatalysis, different types of current Ni/Fe‐based compounds for OER are summarized. The mechanism studies of the active phases and positions of Ni/Fe‐based micro/nanostructures are further introduced to understand the properties of catalytic active sites, which could facilitate further improving the performance of Ni/Fe‐based OER electrocatalysts. Second, splitting water using sunlight with low overpotential is another important target in making solar‐to‐hydrogen micro/nanodevices, and thus attention is then focused on the development of several important Ni/Fe‐based PEC catalysts. Third, the recent theoretical calculations on the OER mechanism during water splitting and insights into electronic structures are analyzed; finally, the future trends and perspectives are also discussed briefly.     

Scalable Triple Cation Mixed Halide Perovskite–BiVO4 Tandems for Bias‐Free Water Splitting

Strong interest exists in the development of organic–inorganic lead halide perovskite photovoltaics and of photoelectrochemical (PEC) tandem absorber systems for solar fuel production. However, their scalability and durability have long been limiting factors. In this work, it is revealed how both fields can be seamlessly merged together, to obtain scalable, bias‐free solar water splitting tandem devices. For this purpose, state‐of‐the‐art cesium formamidinium methylammonium (CsFAMA) triple cation mixed halide perovskite photovoltaic cells with a nickel oxide (NiO_x) hole transport layer are employed to produce Field's metal‐epoxy encapsulated photocathodes. Their stability (up to 7 h), photocurrent density (–12.1 ± 0.3 mA cm^?2 at 0 V versus reversible hydrogen electrode, RHE), and reproducibility enable a matching combination with robust BiVO₄ photoanodes, resulting in 0.25 cm² PEC tandems with an excellent stability of up to 20 h and a bias‐free solar‐to‐hydrogen efficiency of 0.35 ± 0.14%. The high reliability of the fabrication procedures allows scaling of the devices up to 10 cm², with a slight decrease in bias‐free photocurrent density from 0.39 ± 0.15 to 0.23 ± 0.10 mA cm^?2 due to an increasing series resistance. To characterize these devices, a versatile 3D‐printed PEC cell is also developed.     

A Tannic Acid–Derived N‐, P‐Codoped Carbon‐Supported Iron‐Based Nanocomposite as an Advanced Trifunctional Electrocatalyst for the Overall Water Splitting Cells and Zinc–Air Batteries

Rational design and construction of a multifunctional electrocatalyst featuring with high efficiency and low cost is fundamentally important to realize new energy technologies. Herein, a trifunctional electrocatalyst composed of FeP_x nanoparticles and Fe–N–C moiety supported on the N‐, P‐codoped carbon (NPC) is masterly synthesized by a facile one‐pot pyrolysis of the mixture of tannic acid, ferrous chloride, and sodium hydrogen phosphate. The synergy of each component in the FeP_x/Fe–N–C/NPC catalyst renders high catalytic activities and excellent durability toward both oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The electrocatalytic performance and practicability of the robust FeP_x/Fe–N–C/NPC catalyst are further investigated under the practical operation conditions. Particularly, the overall water splitting cell assembled by the FeP_x/Fe–N–C/NPC catalyst only requires a voltage of 1.58 V to output the benchmark current density of 10 mA cm^?2, which is superior to that of IrO₂–Pt/C‐based cell. Moreover, the FeP_x/Fe–N–C/NPC‐based zinc–air batteries deliver high round‐trip efficiency and remarkable cycling stability, much better than that of Pt/C–IrO₂ pair‐based batteries. This work offers a new strategy to design and synthesize highly effective multifunctional electrocatalysts using cheaper tannic acid derived carbon as support applied in electrochemical energy devices.