Molecular‐Level Design of Hierarchically Porous Carbons Codoped with Nitrogen and Phosphorus Capable of In Situ Self‐Activation for Sustainable Energy Systems

Hierarchically porous carbons are attracting tremendous attention in sustainable energy systems, such as lithium ion battery (LIB) and fuel cell, due to their excellent transport properties that arise from the high surface area and rich porosity. The state‐of‐the‐art approaches for synthesizing hierarchically porous carbons normally require chemical‐ and/or template‐assisted activation techniques, which is complicate, time consuming, and not feasible for large scale production. Here, a molecular‐level design principle toward large‐scale synthesis of nitrogen and phosphorus codoped hierarchically porous carbon (NPHPC) through an in situ self‐activation process is proposed. The material is fabricated based on the direct pyrolysis of a well‐designed polymer, melamine polyphosphate, which is capable of in situ self‐activation to generate large specific surface area (1479 m² g^?1) and hierarchical pores in the final NPHPC. As an anode material for LIB, NPHPC delivers a high reversible capacity of 1073 mAh g^?1 and an excellent cyclic stability for 300 cycles with negligible capacity decay. The peculiar structural properties and synergistic effect of N and P codopants also enable NPHPC a promising electrocatalyst for oxygen reduction reaction, a key cathodic reaction process of many energy conversion devices (for example, fuel cells and metal air batteries). Electrochemical measurements show NPHPC a comparable electrocatalytic performance to commercial Pt/C catalyst (onset potential of 0.88 V vs reversible hydrogen electrode in alkaline medium) with excellent stability (89.8% retention after 20 000 s continuous operation) and superior methanol tolerance.     

Three‐Dimensional Self‐Supported Metal Oxides for Advanced Energy Storage

The miniaturization of power sources aimed at integration into micro‐ and nano‐electronic devices is a big challenge. To ensure the future development of fully autonomous on‐board systems, electrodes based on self‐supported 3D nanostructured metal oxides have become increasingly important, and their impact is particularly significant when considering the miniaturization of energy storage systems. This review describes recent advances in the development of self‐supported 3D nanostructured metal oxides as electrodes for innovative power sources, particularly Li‐ion batteries and electrochemical supercapacitors. Current strategies for the design and morphology control of self‐supported electrodes fabricated using template, lithography, anodization and self‐organized solution techniques are outlined along with different efforts to improve the storage capacity, rate capability, and cyclability.     

Mesoporous Hollow Sb/ZnS@C Core–Shell Heterostructures as Anodes for High‐Performance Sodium‐Ion Batteries

Combining the advantage of metal, metal sulfide, and carbon, mesoporous hollow core–shell Sb/ZnS@C hybrid heterostructures composed of Sb/ZnS inner core and carbon outer shell are rationally designed based on a robust template of ZnS nanosphere, as anodes for high‐performance sodium‐ion batteries (SIBs). A partial cation exchange reaction based on the solubility difference between Sb₂S₃ and ZnS can transform mesoporous ZnS to Sb₂S₃/ZnS heterostructure. To get a stable structure, a thin contiguous resorcinol‐formaldehyde (RF) layer is introduced on the surface of Sb₂S₃/ZnS heterostructure. The effectively protective carbon layer from RF can be designed as the reducing agent to convert Sb₂S₃ to metallic Sb to obtain core–shell Sb/ZnS@C hybrid heterostructures. Simultaneously, the carbon outer shell is beneficial to the charge transfer kinetics, and can maintain the structure stability during the repeated sodiation/desodiation process. Owing to its unique stable architecture and synergistic effects between the components, the core–shell porous Sb/ZnS@C hybrid heterostructure SIB anode shows a high reversible capacity, good rate capability, and excellent cycling stability by turning the optimized voltage range. This novel strategy to prepare carbon‐layer‐protected metal/metal sulfide core–shell heterostructure can be further extended to design other novel nanostructured systems for high‐performance energy storage devices.     

Oxygen Vacancy–Rich In‐Doped CoO/CoP Heterostructure as an Effective Air Cathode for Rechargeable Zn–Air Batteries

An efficient and low‐cost electrocatalyst for reversible oxygen electrocatalysis is crucial for improving the performance of rechargeable metal?air batteries. Herein, a novel oxygen vacancy–rich 2D porous In‐doped CoO/CoP heterostructure (In‐CoO/CoP FNS) is designed and developed by a facile free radicals–induced strategy as an effective bifunctional electrocatalyst for rechargeable Zn–air batteries. The electron spin resonance and X‐ray absorption near edge spectroscopy provide clear evidence that abundant oxygen vacancies are formed in the interface of In‐CoO/CoP FNS. Owing to abundant oxygen vacancies, porous heterostructure, and multiple components, In‐CoO/CoP FNS exhibits excellent oxygen reduction reaction activity with a positive half‐wave potential of 0.81 V and superior oxygen evolution reaction activity with a low overpotential of 365 mV at 10 mA cm^?2. Moreover, a home‐made Zn–air battery with In‐CoO/CoP FNS as an air cathode delivers a large power density of 139.4 mW cm^?2, a high energy density of 938 Wh kg_Zn^?1, and can be steadily cycled over 130 h at 10 mA cm^?2, demonstrating great application potential in rechargeable metal–air batteries.     

Hierarchically Porous W‐Doped CoP Nanoflake Arrays as Highly Efficient and Stable Electrocatalyst for pH‐Universal Hydrogen Evolution

It is still challenging to develop high‐efficiency and low‐cost non‐noble metal‐based electrocatalysts for hydrogen evolution reaction (HER) in pH‐universal electrolytes. Herein, hierarchically porous W‐doped CoP nanoflake arrays on carbon cloth (W‐CoP NAs/CC) are synthesized via facile liquid‐phase reactions and a subsequent phosphorization process. The W‐CoP NAs/CC hybrid can be directly employed as a binder‐free electrocatalyst and delivers superior HER performance in pH‐universal electrolytes. Especially, it delivers very low overpotentials of 89, 94, and 102 mV to reach a current density of 10 mA cm^–2 in acidic, alkaline, and neutral electrolytes, respectively. Furthermore, it shows a nearly 100% Faradaic efficiency as well as superior long‐term stability with no decreasing up to 36 h in pH‐universal electrolytes. The outstanding electrocatalytic performance of W‐CoP NAs/CC can be mainly attributed to the porous W‐doped nanoflake arrays, which not only afford rich exposed active sites, but also accelerate the access of electrolytes and the diffusion of H₂ bubbles, thus efficiently promoting the HER performance. This work provides a new horizon to rationally design and synthesize highly effective and stable non‐noble metal phosphide‐based pH‐universal electrocatalysts for HER.     

A Liquid‐Metal‐Enabled Versatile Organic Alkali‐Ion Battery

Despite the high specific capacity and low redox potential of alkali metals, their practical application as anodes is still limited by the inherent dendrite‐growth problem. The fusible sodium–potassium (Na–K) liquid metal alloy is an alternative that detours this drawback, but the fundamental understanding of charge transport in this binary electroactive alloy anode remains elusive. Here, comprehensive characterization, accompanied with density function theory (DFT) calculations, jointly expound the Na–K anode‐based battery working mechanism. With the organic cathode sodium rhodizonate dibasic (SR) that has negligible selectivity toward cations, the charge carrier is screened by electrolytes due to the selective ionic pathways in the solid electrolyte interphase (SEI). Stable cycling for this Na–K/SR battery is achieved with capacity retention per cycle to be 99.88% as a sodium‐ion battery (SIB) and 99.70% as a potassium‐ion battery (PIB) for over 100 cycles. Benefitting from the flexibility of the liquid metal and the specially designed carbon nanofiber (CNF)/SR layer‐by‐layer cathode, a flexible dendrite‐free alkali‐ion battery is achieved with an ultrahigh areal capacity of 2.1 mAh cm^?2. Computation‐guided materials selection, characterization‐supported mechanistic understanding, and self‐validating battery performance collectively promise the prospect of a high‐performance, dendrite‐free, and versatile organic‐based liquid metal battery.     

Self‐Phosphorization of MOF‐Armored Microbes for Advanced Energy Storage

Utilization of microbes as the carbon source and structural template to fabricate porous carbon has incentivized great interests owing to their diverse micromorphology and intricate intracellular structure, apart from the obvious benefit of “turning waste into wealth.” Challenges remain to preserve the biological structure through the harsh and laborious post‐synthetic treatments, and tailor the functionality as desired. Herein, Escherichia coli is directly coated with metal–organic frameworks (MOFs) through in situ assembly to fabricate N, P co‐doped porous carbon capsules expressing self‐phosphorized metal phosphides. While the MOF coating serves as an armoring layer for facilitating the morphology inheritance from the bio‐templates and provides metal sources for generating extra porosity and electrochemically active sites, the P‐rich phospholipids and N‐rich proteins from the plasma membrane enable carbon matrix doping and further yield metal phosphides. These unique structural and compositional features endow the carbon capsules with great capabilities in suppressing polysulfide shuttling and catalyzing reversible oxygen conversion, ultimately leading to the superb performance of lithium–sulfur batteries and zinc–air batteries. Combining the bio‐templating strategy with hierarchical MOF assembly, this work opens a new avenue for the fabrication of highly porous and functional carbon for advanced energy applications.     

General Construction of 2D Ordered Mesoporous Iron‐Based Metal–Organic Nanomeshes

Nanomeshes with highly regular, permeable pores in plane, combining the exceptional porous architectures with intrinsic properties of 2D materials, have attracted increasing attention in recent years. Herein, a series of 2D ultrathin metal–organic nanomeshes with ordered mesopores is obtained by a self‐assembly method, including metal phosphate and metal phosphonate. The resultant mesoporous ferric phytate nanomeshes feature unique 2D ultrathin monolayer morphologies ( ≈ 9 nm thickness), hexagonally ordered, permeable mesopores of ≈ 16 nm, as well as improved surface area and pore volume. Notably, the obtained ferric phytate nanomeshes can directly in situ convert into mesoporous sulfur‐doped metal phosphonate nanomeshes by serving as an unprecedented reactive self‐template. Furthermore, as advanced anode materials for Li‐ion batteries, they deliver excellent capacity, good rate capability, and cycling performance, greatly exceeding the similar metal phosphate‐based materials reported previously, resulting from their unique 2D ultrathin mesoporous structure. Therefore, the work will pave an avenue for constructing the other 2D ordered mesoporous materials, and thus offer new opportunities for them in diverse areas.     

Self‐Supported and Flexible Sulfur Cathode Enabled via Synergistic Confinement for High‐Energy‐Density Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have attracted much attention in the field of electrochemical energy storage due to their high energy density and low cost. However, the “shuttle effect” of the sulfur cathode, resulting in poor cyclic performance, is a big barrier for the development of Li–S batteries. Herein, a novel sulfur cathode integrating sulfur, flexible carbon cloth, and metal–organic framework (MOF)‐derived N‐doped carbon nanoarrays with embedded CoP (CC@CoP/C) is designed. These unique flexible nanoarrays with embedded polar CoP nanoparticles not only offer enough voids for volume expansion to maintain the structural stability during the electrochemical process, but also promote the physical encapsulation and chemical entrapment of all sulfur species. Such designed CC@CoP/C cathodes with synergistic confinement (physical adsorption and chemical interactions) for soluble intermediate lithium polysulfides possess high sulfur loadings (as high as 4.17 mg cm^–2) and exhibit large specific capacities at different C‐rates. Specially, an outstanding long‐term cycling performance can be reached. For example, an ultralow decay of 0.016% per cycle during the whole 600 cycles at a high current density of 2C is displayed. The current work provides a promising design strategy for high‐energy‐density Li–S batteries.     

Hierarchical TiO2/SnO2 Hollow Spheres Coated with Graphitized Carbon for High‐Performance Electrochemical Li‐Ion Storage

A self‐templated strategy is developed to fabricate hierarchical TiO₂/SnO₂ hollow spheres coated with graphitized carbon (HTSO/GC‐HSs) by combined sol–gel processes with hydrothermal treatment and calcination. The as‐prepared mesoporous HTSO/GC‐HSs present an approximate yolk‐double–shell structure, with high specific area and small nanocrystals of TiO₂ and SnO₂, and thus exhibit superior electrochemical reactivity and stability when used as anode materials for Li‐ion batteries. A high reversible specific capacity of about 310 mAh g^?1 at a high current density of 5 A g^?1 can be achieved over 500 cycles indicating very good cycle stability and rate performance.     

MOF‐Based Metal‐Doping‐Induced Synthesis of Hierarchical Porous CuN/C Oxygen Reduction Electrocatalysts for Zn–Air Batteries

A transition‐metal–nitrogen/carbon (TM–N/C, TM = Fe, Co, Ni, etc.) system is a popular, nonprecious‐metal oxygen reduction reaction (ORR) electrocatalyst for fuel cell and metal–air battery applications. However, there remains a lack of comprehensive understanding about the ORR electrocatalytic mechanism on these catalysts, especially the roles of different forms of metal species on electrocatalytic performance. Here, a novel Cu?N/C ORR electrocatalyst with a hybrid Cu coordination site is successfully fabricated with a simple but efficient metal–organic‐framework‐based, metal‐doping‐induced synthesis strategy. By directly pyrolyzing Cu‐doped zeolitic‐imidazolate‐framework‐8 polyhedrons, the obtained Cu?N/C catalyst can achieve a high specific surface area of 1182 m² g^?1 with a refined hierarchical porous structure and a high surface N content of 11.05 at%. Moreover, regulating the Cu loading can efficiently tune the states of Cu(II) and Cu⁰, resulting in the successful construction of a highly active hybrid coordination site of N?Cu(II)?Cu⁰ in derived Cu?N/C catalysts. As a result, the optimized 25% Cu?N/C catalyst possesses a high ORR activity and stability in 0.1 m KOH solution, as well as excellent performance and stability in a Zn–air battery.     

Cobalt Phosphide Composite Encapsulated within N,P‐Doped Carbon Nanotubes for Synergistic Oxygen Evolution

Exploring highly efficient and stable oxygen evolution reaction (OER) electrocatalysts such as transition‐metal phosphides (TMPs) is critical to advancing renewable hydrogen fuel. TMP nanostructures typically involving binary or ternary TMPs tuned by cation or anion doping are suggested to be promising low‐cost and durable OER catalysts. Herein, the preparation of CoP/CoP₂ composite nanoparticles encapsulated within N,P‐doped carbon nanotubes (CoP/CoP₂@NPCNTs) is demonstrated as a synergistic electrocatalyst for OER via the calcination of a CoAl‐layered double hydroxide/melamine mixture and subsequent phosphorization. Facile visualization by scanning electron microscopy in conjunction with electron backscatter diffraction demonstrates the encapsulation of the CoP/CoP₂ nanoparticles within the N,P‐codoped CNTs. Electrocatalytic evaluation shows that the composite electrode requires a low overpotential of 300 mV for the OER at 10 mA cm^?2 in a 1.0 m KOH solution and, in particular, exhibits an excellent long‐term durability of ≈100 h, which is superior to that of the state‐of‐the‐art RuO₂ electrocatalyst. Density functional theory calculations reveal that the synergistic effect of CoP and CoP₂ can enhance the electrocatalytic performance. In addition, molecular dynamics simulations demonstrate that the generated O₂ molecules can readily diffuse out of the CNTs. Both the effects give rise to the observed OER enhancement.     

Novel 3D Nanoporous Zn–Cu Alloy as Long‐Life Anode toward High‐Voltage Double Electrolyte Aqueous Zinc‐Ion Batteries

The recharge ability of zinc metal‐based aqueous batteries is greatly limited by the zinc anode. The poor cycling durability of Zn anodes is attributed to the dendrite growth, shape change and passivation, but this issue has been ignored by using an excessive amount of Zn in the past. Herein, a 3D nanoporous (3D NP) Zn–Cu alloy is fabricated by a sample electrochemical‐assisted annealing thermal method combined, which can be used directly as self‐supported electrodes applied for renewable zinc‐ion devices. The 3D NP architectures electrode offers high electron and ion transport paths and increased material loading per unit substrate area, which can uniformly deposit/strip Zn and improve charge storage ability. Benefiting from the intrinsic materials and architectures features, the 3D NP Zn–Cu alloy anode exhibits high areal capacity and excellent cycling stability. Further, the fabricated high‐voltage double electrolyte aqueous Zn–Br₂ battery can deliver maximum areal specific capacity of ≈1.56 mAh cm^?2, which is close to the level of typical commercial Li‐ion batteries. The excellent performance makes it an ideal candidate for next‐generation aqueous zinc‐ion batteries.     

Cobalt Phosphides Nanocrystals Encapsulated by P‐Doped Carbon and Married with P‐Doped Graphene for Overall Water Splitting

As one class of important functional materials, transition metal phosphides (TMPs) nanostructures show promising applications in catalysis and energy storage fields. Although great progress has been achieved, phase‐controlled synthesis of cobalt phosphides nanocrystals or related nanohybrids remains a challenge, and their use in overall water splitting (OWS) is not systematically studied. Herein, three kinds of cobalt phosphides nanocrystals encapsulated by P‐doped carbon (PC) and married with P‐doped graphene (PG) nanohybrids, including CoP@PC/PG, CoP‐Co₂P@PC/PG, and Co₂P@PC/PG, are obtained through controllable thermal conversion of presynthesized supramolecular gels that contain cobalt salt, phytic acid, and graphene oxides at proper temperature under Ar/H₂ atmosphere. Among them, the mixed‐phase CoP‐Co₂P@PC/PG nanohybrids manifest high electrocatalytic activity toward both hydrogen and oxygen evolution in alkaline media. Remarkably, using them as bifunctional catalysts, the fabricated CoP‐Co₂P@PC/PG || CoP‐Co₂P@PC/PG electrolyzer only needs a cell voltage of 1.567 V for driving OWS to reach the current density at 10 mA cm^?2, superior to their pure‐phase counterparts and recently reported bifunctional catalysts based devices. Also, such a CoP‐Co₂P@PC/PG || CoP‐Co₂P@PC/PG device exhibits outstanding stability for OWS. This work may shed some light on optimizing TMPs nanostructures based on phase engineering, and promote their applications in OWS or other renewable energy options.     

Coordination‐Induced Interlinked Covalent‐ and Metal–Organic‐Framework Hybrids for Enhanced Lithium Storage

Covalent organic frameworks (COF) or metal–organic frameworks have attracted significant attention for various applications due to their intriguing tunable micro/mesopores and composition/functionality control. Herein, a coordination‐induced interlinked hybrid of imine‐based covalent organic frameworks and Mn‐based metal–organic frameworks (COF/Mn‐MOF) based on the Mn? N bond is reported. The effective molecular‐level coordination‐induced compositing of COF and MOF endows the hybrid with unique flower‐like microsphere morphology and superior lithium‐storage performances that originate from activated Mn centers and the aromatic benzene ring. In addition, hollow or core–shell MnS trapped in N and S codoped carbon (MnS@NS‐C‐g and MnS@NS‐C‐l) are also derived from the COF/Mn‐MOF hybrid and they exhibit good lithium‐storage properties. The design strategy of COF–MOF hybrid can shed light on the promising hybridization on porous organic framework composites with molecular‐level structural adjustment, nano/microsized morphology design, and property optimization.     

Hierarchical Porous Nanosheets Constructed by Graphene‐Coated,Interconnected TiO2 Nanoparticles for Ultrafast Sodium Storage

Sodium‐ion batteries (SIBs) are considered promising next‐generation energy storage devices. However, a lack of appropriate high‐performance anode materials has prevented further improvements. Here, a hierarchical porous hybrid nanosheet composed of interconnected uniform TiO₂ nanoparticles and nitrogen‐doped graphene layer networks (TiO₂@NFG HPHNSs) that are synthesized using dual‐functional C₃N₄ nanosheets as both the self‐sacrificing template and hybrid carbon source is reported. These HPHNSs deliver high reversible capacities of 146 mA h g^?1 at 5 C for 8000 cycles, 129 mA h g^?1 at 10 C for 20 000 cycles, and 116 mA h g^?1 at 20 C for 10 000 cycles, as well as an ultrahigh rate capability up to 60 C with a capacity of 101 mA h g^?1. These results demonstrate the longest cyclabilities and best rate capability ever reported for TiO₂‐based anode materials for SIBs. The unprecedented sodium storage performance of the TiO₂@NFG HPHNSs is due to their unique composition and hierarchical porous 2D structure.     

FeP@C Nanotube Arrays Grown on Carbon Fabric as a Low Potential and Freestanding Anode for High‐Performance Li‐Ion Batteries

An anode of self‐supported FeP@C nanotube arrays on carbon fabric (CF) is successfully fabricated via a facile template‐based deposition and phosphorization route: first, well‐aligned FeOOH nanotube arrays are simply obtained via a solution deposition and in situ etching route with hydrothermally crystallized (Co,Ni)(CO₃)_0.5OH nanowire arrays as the template; subsequently, these uniform FeOOH nanotube arrays are transformed into robust carbon‐coated Fe₃O₄ (Fe₃O₄@C) nanotube arrays via glucose adsorption and annealing treatments; and finally FeP@C nanotube arrays on CF are achieved through the facile phosphorization of the oxide‐based arrays. As an anode for lithium‐ion batteries (LIBs), these FeP@C nanotube arrays exhibit superior rate capability (reversible capacities of 945, 871, 815, 762, 717, and 657 mA h g⁻¹ at 0.1, 0.2, 0.4, 0.8, 1.3, and 2.2 A g⁻¹, respectively, corresponding to area specific capacities of 1.73, 1.59, 1.49, 1.39, 1.31, 1.20 mA h cm⁻² at 0.18, 0.37, 0.732, 1.46, 2.38, and 4.03 mA cm⁻², respectively) and a stable long‐cycling performance (a high specific capacity of 718 mA h g⁻¹ after 670 cycles at 0.5 A g⁻¹, corresponding to an area capacity of 1.31 mA h cm⁻² at 0.92 mA cm⁻²).     

Flexible 3D Porous MXene Foam for High‐Performance Lithium‐Ion Batteries

2D transition‐metal carbides and nitrides, named MXenes, are promising materials for energy storage, but suffer from aggregation and restacking of the 2D nanosheets, which limits their electrochemical performance. In order to overcome this problem and realize the full potential of MXene nanosheets, a 3D MXene foam with developed porous structure is established via a simple sulfur‐template method, which is freestanding, flexible, and highly conductive, and can be directly used as the electrode in lithium‐ion batteries. The 3D porous architecture of the MXene foam offers massive active sites to enhance the lithium storage capacity. Moreover, its foam structure facilitates electrolyte infiltration for fast Li⁺ transfer. As a result, this flexible 3D porous MXene foam exhibits significantly enhanced capacity of 455.5 mAh g^?1 at 50 mA g^?1, excellent rate performance (101 mAh g^?1 at 18 A g^?1), and superior ultralong‐term cycle stability (220 mAh g^?1 at 1 A g^?1 after 3500 cycles). This work not only demonstrates the great superiority of the 3D porous MXene foam but also proposes the sulfur‐template method for controllable constructing of the 3D foam from 2D nanosheets at a relatively low temperature.     

Self‐Template‐Directed Metal–Organic Frameworks Network and the Derived Honeycomb‐Like Carbon Flakes via Confinement Pyrolysis

Metal–organic frameworks (MOFs) have become a research hotspot since they have been explored as convenient precursors for preparing various multifunctional nanomaterials. However, the preparation of MOF networks with controllable flake morphology in large scale is not realized yet. Herein, a self‐template strategy is developed to prepare MOF networks. In this work, layered double‐metal hydroxide (LDH) and other layered metal hydroxides are used not only as a scaffold but also as a self‐sacrificed metal source. After capturing the abundant metal cations identically from the LDH by the organic linkers, MOF networks are in situ formed. It is interesting that the MOF network‐derived carbon materials retain the flake morphology and exhibit a unique honeycomb‐like macroporous structure due to the confined shrinkage of the polyhedral facets. The overall properties of the carbon networks are adjustable according to the tailored metal compositions in LDH and the derived MOFs, which are desirable for target‐oriented applications as exemplified by the electrochemical application in supercapacitors.     

MOF‐Derived Bifunctional Cu3P Nanoparticles Coated by a N,P‐Codoped Carbon Shell for Hydrogen Evolution and Oxygen Reduction

Metal–organic frameworks (MOFs) have recently emerged as a type of uniformly and periodically atom‐distributed precursor and efficient self‐sacrificial template to fabricate hierarchical porous‐carbon‐related nanostructured functional materials. For the first time, a Cu‐based MOF, i.e., Cu‐NPMOF is used, whose linkers contain nitrogen and phosphorus heteroatoms, as a single precursor and template to prepare novel Cu₃P nanoparticles (NPs) coated by a N,P‐codoped carbon shell that is extended to a hierarchical porous carbon matrix with identical uniform N and P doping (termed Cu₃P@NPPC) as an electrocatalyst. Cu₃P@NPPC demonstrates outstanding activity for both the hydrogen evolution and oxygen reduction reaction, representing the first example of a Cu₃P‐based bifunctional catalyst for energy‐conversion reactions. The high performances are ascribed to the high specific surface area, the synergistic effects of the Cu₃P NPs with intrinsic activity, the protection of the carbon shell, and the hierarchical porous carbon matrix doped by multiheteroatoms. This strategy of using a diverse MOF as a structural and compositional material to create a new multifunctional composite/hybrid may expand the opportunities to explore highly efficient and robust non‐noble‐metal catalysts for energy‐conversion reactions.