Manipulating Bubbles in Aqueous Environment via a Lubricant‐Infused Slippery Surface

Designing functional interfaces to control solid/fluid interactions has emerged as an indispensable strategy for developing advanced materials and optimizing current technologies. Surfaces exhibiting special wettability offer many paradigms for regulating fluid behavior in practical applications including oil–water separation and fog harvesting. Nevertheless, the flexible manipulation of air bubbles under water still has room for further exploration. Here, it is reported that the lubricant‐infused slippery (LIS) surface with water repellency is applicable to manipulate bubbles in an aqueous environment. On the basis of the sufficient bubble adhesion, the shaped LIS tracks can be used in guiding the bubble delivery and facilitating continuous bubble distribution. Through the incorporation of an asymmetrical structure into the LIS surface, a triangle‐shaped bubble holder is capable of controlling a single bubble with ease. Moreover, the LIS surface is integrated with a H₂ microbubble evolving apparatus, demonstrating a potential method for in situ capture and delivery of microbubbles. The current finding reveals the meaningful interaction between underwater bubbles and the LIS surface, providing several examples for the applications of this bubble carrier, which should shed new light on the development of bubble‐controlling interfaces.     

Revisiting Metal Sulfide Semiconductors: A Solution‐Based General Protocol for Thin Film Formation,Hall Effect Measurement,and Application Prospects

Nanostructured thin films of metal sulfides (MS) are highly desirable materials for various optoelectronic device applications. However, a general low‐temperature protocol that describes deposition of varieties of MS structures, especially in their film form is still not available in literatures. Here, a simple and highly effective general solution‐based deposition protocol for highly crystalline and well‐defined nanostructured MS thin films from ethanol on variety of conducting and non‐conducting substrates is presented. The films display remarkable electronic properties such as high carrier mobility and high conductivity. When NiS thin film deposited on a flexible polyethylene terephthalate (PET) substrate is used as a fluorine doped tin oxide (FTO)‐free counter electrode in dye‐sensitized solar cells, it exhibits a solar‐to‐electric power conversion efficiency of 9.27 ± 0.26% with the highest conversion efficiency as high as 9.50% (vs 8.97 ± 0.07% exhibited by Pt‐electrode). In addition, the NiS film deposited on a Ti‐foil has demonstrated an outstanding catalytic activity for the hydrogen and oxygen evolution reactions from water.     

Durability test of PVP‐capped Pt nanoclusters counter electrode for highly efficiency dye‐sensitized solar cell

In this paper, the durability of PVP‐capped Pt nanoclusters counter electrode (PVP‐Pt CE) for dye‐sensitized solar cell (DSSC) has been extensively evaluated including electrochemical reaction durability, thermal stress durability and light soaking durability. It is revealed that PVP‐Pt CE exhibits both electrochemical and thermal durability by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) test. Moreover, DSSC containing PVP‐Pt CE shows over 9.37% conversion efficiency in highly volatile electrolyte system. As to device thermal durability, both low‐volatile and non‐volatile electrolyte systems were tested and the results show relative efficiency can maintain more than 85% after accelerated thermal test at 85°C for 1000 h, and 110% after 60°C for 1000 h. Finally, after continuous light soaking test under 60°C for 1000 h, the relative efficiency can still maintain at 94%. Copyright © 2011 John Wiley & Sons, Ltd.     

Nanostructured platinum counter electrodes by self-assembled nanospheres for dye-sensitized solar cells

We report a method to fabricate nanostructured Pt counter electrodes for DSSCs using self-assembly nanosphere monolayers. The spin-coating in combination with the water transfer technique was adopted to produce low-defect, large-area and close-packed (hexagonal) self-assembly nanosphere monolayers on glass substrates. By vacuum deposition of SiO₂ through pores of self-assembly nanosphere monolayers, arrays of SiO₂ nanodots were formed on glass substrates. Further blanket deposition of Pt on such nanostructured substrates gave nanostructured Pt counter electrodes for DSSCs. DSSCs using such nanostructured Pt electrodes showed enhanced short-circuit currents, spectral responses, and power conversion efficiencies, compared to DSSCs using unstructured Pt counter electrodes. Investigations by electrochemical impedance spectroscopy revealed the reduction of charge-transfer resistances for the Pt/electrolyte interface in using nanostructured Pt counter electrodes, due to increase of the active surface areas and thus the electro-catalytic ability (activity).     

A Self‐Standing High‐Performance Hydrogen Evolution Electrode with Nanostructured NiCo2O4/CuS Heterostructures

An efficient self‐standing 3D hydrogen evolution cathode has been developed by coating nickel cobaltite (NiCo₂O₄)/CuS nanowire heterostructures on a carbon fiber paper (CFP). The obtained CFP/NiCo₂O₄/CuS electrode shows exceptional hydrogen evolution reaction (HER) performance and excellent durability in acidic conditions. Remarkably, as an integrated 3D hydrogen‐evolving cathode operating in acidic electrolytes, CFP/NiCo₂O₄/CuS maintains its activity more than 50 h and exhibits an onset overpotential of 31.1 mV, an exchange current density of 0.246 mA cm^?2, and a Tafel slope of 41 mV dec^?1. Compared to other non‐Pt electrocatalysts reported to date, CFP/NiCo₂O₄/CuS exhibits the highest HER activity and can be used in HER to produce H₂ with nearly quantitative faradaic yield in acidic aqueous media with stable activity. Furthermore, by using CFP/NiCo₂O₄/CuS as a self‐standing electrode in a water electrolyzer, a current density of 18 mA cm^?2 can be achieved at a voltage of 1.5 V which can be driven by a single‐cell battery. This strategy provides an effective, durable, and non‐Pt electrode for water splitting and hydrogen generation.     

Ordered Mesoporous Metastable α‐MoC1−x with Enhanced Water Dissociation Capability for Boosting Alkaline Hydrogen Evolution Activity

The sluggish reaction kinetics of the alkaline hydrogen evolution reaction (HER) remains an important challenge for water–alkali electrolyzers, which originates predominantly from the additional water dissociation step required for the alkaline HER. In this work, it is demonstrated theoretically and experimentally that metastable, face‐centered‐cubic α‐MoC_1?x phase shows superior water dissociation capability and alkaline HER activity than stable, hexagonal‐close‐packed Mo₂C phase. Next, high surface area ordered mesoporous α‐MoC_1?x (MMC) is designed via a nanocasting method. In MMC structure, the α‐MoC_1?x phase facilitates the water dissociation reaction, while the mesoporous structure with high surface area enables a high dispersion of metal NPs and efficient mass transport. As a result, Pt nanoparticles (NPs) supported on MMC (Pt/MMC) show substantially enhanced alkaline HER activity in terms of overpotentials, Tafel slopes, mass and specific activities, and exchange current densities, compared to commercial Pt/C and Pt NPs supported on particulate α‐MoC_1?x or β‐Mo₂C. Notably, Pt/MMC shows very low Tafel slope of 30 mV dec^–1, which is the lowest value among the reported Pt‐based alkaline HER catalysts, suggesting the critical role of MMC in enhancing the HER kinetics. The promotional effect of MMC support in the alkaline HER is further demonstrated with an Ir/MMC catalyst.     

Rationally Engineered Electrodes for a High‐Performance Solid‐State Cable‐Type Supercapacitor

Wire‐shaped electrodes for solid‐state cable‐type supercapacitors (SSCTS) with high device capacitance and ultrahigh rate capability are prepared by depositing poly(3,4‐ethylenedioxythiophene) onto self‐doped TiO₂ nanotubes (D‐TiO₂) aligned on Ti wire via a well‐controlled electrochemical process. The large surface area, short ion diffusion path, and high electrical conductivity of these rationally engineered electrodes all contribute to the energy storage performance of SSCTS. The cyclic voltammetric studies show the good energy storage ability of the SSCTS even at an ultrahigh scan rate of 1000 V s^?1, which reveals the excellent instantaneous power characteristics of the device. The capacitance of 1.1 V SSCTS obtained from the charge–discharge measurements is 208.36 µF cm^?1 at a discharge current of 100 µA cm^?1 and 152.36 µF cm^?1 at a discharge current of 2000 µA cm^?1, respectively, indicating the ultrahigh rate capability. Furthermore, the SSCTS shows superior cyclic stability during long‐term (20 000 cycles) cycling, and also maintains excellent performance when it is subjected to bending and succeeding straightening process.     

Vertical 2D MoO2/MoSe2 Core–Shell Nanosheet Arrays as High‐Performance Electrocatalysts for Hydrogen Evolution Reaction

Electrochemical water splitting is very attractive for green fuel energy production, but the development of active, stable, and earth‐abundant catalysts for the hydrogen evolution reaction (HER) remains a major challenge. Here, core–shell nanostructured architectures are used to design and fabricate efficient and stable HER catalysts from earth‐abundant components. Vertically oriented quasi‐2D core–shell MoO₂/MoSe₂ nanosheet arrays are grown onto insulating (SiO₂/Si wafer) or conductive (carbon cloth) substrates. This core–shell nanostructure array architecture exhibits synergistic properties to create superior HER performance, where high density structural defects and disorders on the shell generated by a large crystalline mismatch of MoO₂ and MoSe₂ act as multiple active sites for HER, and the metallic MoO₂ core facilitates charge transport for proton reduction while the vertical nanosheet arrays ensure fully exposed active sites toward electrolytes. As a HER catalyst, this electrode exhibits a low Tafel slope of 49.1 mV dec^?1, a small onset potential of 63 mV, and an ultralow charge transfer resistance (R_ct) of 16.6 Ω at an overpotential of 300 mV with a long cycling durability for up to 8 h. This work suggests that a quasi 2D core–shell nanostructure combined with a vertical array microstructure is a promising strategy for efficient water splitting electrocatalysts with scale‐up potential.     

Few Layered N,P Dual‐Doped Carbon‐Encapsulated Ultrafine MoP Nanocrystal/MoP Cluster Hybrids on Carbon Cloth: An Ultrahigh Active and Durable 3D Self‐Supported Integrated Electrode for Hydrogen Evolution Reaction in a Wide pH Range

Development of highly active and stable electrocatalysts is a key to realize efficient hydrogen evolution through water electrolysis. Here, the development of a 3D self‐supported integrated electrode constituting few layered N, P dual‐doped carbon‐encapsulated ultrafine MoP nanocrystal/MoP cluster hybrids on carbon cloth (FLNPC@MoP‐NC/MoP‐C/CC) is demonstrated. Benefiting from novel structural features including fully open and accessible nanoporosity, ultrasmall size of MoP‐NCs on MoP‐Cs as well as strong synergistic effects of N, P dual‐doped carbon layers with MoP‐NCs, the FLNPC@MoP‐NC/MoP‐C/CC as a 3D self‐supported binder‐free integrated electrode exhibits extraordinary catalytic activity for the hydrogen evolution reaction (HER) with extremely low overpotentials at all pH values ( j = 10 mA cm^?2 at η = 74, 106, and 69 mV in 0.5 m H₂SO₄, 1.0 m PBS, and 1.0 m KOH electrolytes, respectively). To the best of our knowledge, the ultrahigh electrocatalytic performance represents one of the best MoP‐based HER electrocatalysts reported so far. Additionally, few layered N, P dual‐doped carbon can effectively prevent MoP‐NC/MoP‐C from corrosion, making the FLNPC@MoP‐NC/MoP‐C/CC exhibit nearly unfading stability after 50 h testing in acidic, neutral, and alkaline media, which shows great promise for electrocatalytic water splitting application.     

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.     

Protein/Polymer‐Based Dual‐Responsive Gold Nanoparticles with pH‐Dependent Thermal Sensitivity

This article presents the synthesis and physicochemical behavior of dual‐responsive plasmonic nanoparticles with reversible optical properties based on protein‐coated gold nanoparticles grafted with thermosensitive polymer brushes by means of surface‐initiated atom transfer radical polymerization (SI‐ATRP) that exhibit pH‐dependent thermo‐responsive behavior. Spherical gold NPs of two different sizes (15 nm and 60 nm) and with different stabilizing agents (citrate and cetyltrimethylammonium bromide (CTAB), respectively) were first capped with bovine serum albumin (BSA). The resulting BSA‐capped NPs (Au@BSA NPs) exhibited not only extremely high colloidal stability under physiological conditions, but also a reversible U‐shaped pH‐responsive behavior, similar to pure BSA. The ?‐amine of the L‐lysine in the protein coating was then used to covalently bind an ATRP‐initiator, allowing for the SI‐ATRP of thermosensitive polymer brushes of oligo(ethylene glycol) methacrylates with an LCST of 42 °C in pure water and around 37 °C under physiological conditions. Such protein coated nanoparticles grafted with thermosensitive polymers exhibit a smart pH‐dependent thermosensitive behavior.     

Anisotropic Wettability of Biomimetic Micro/Nano Dual‐Scale Inclined Cones Fabricated by Ferrofluid‐Molding Method

Learning from nature, a series of cone‐shaped structures resembling trichomes of plants are fabricated by ferrofluid molding to understand the influence of geometry on wettability. Experimentally, ferrofluid microdroplets are generated under an external magnetic field, and their shape can be changed from right cones into oblique cones by tilting the external magnetic field. Followed by hard molds made with UV‐curable tri(propylene glycol) diacrylate, polydimethylsiloxane microcones with different inclination angle (θ) are subsequently generated. Nickel thin film is deposited onto the microcones to form micro/nano dual‐scale structures. The largest contact angle (CA) is obtained in nickel‐deposited right cones (CA = 163.1° ± 2.5°). Anisotropic wettability is exhibited in oblique cones and the retention forces in the pin and release directions differ up to 12 μN (cones θ = 50°). As explained by a model as a function of the inclination angle of the cone structures, the contact and retention forces of droplet move in pin and release directions exhibit considerable differences. Results suggest the inclination of the trichomes assist the balance between repellency and retention of water in a direction‐selective manner.     

Biomimetic and Superwettable Nanofibrous Skins for Highly Efficient Separation of Oil‐in‐Water Emulsions

Developing a feasible and efficient separation membrane for the purification of highly emulsified oily wastewater is of significance but challenging due to the critical limitations of low flux and serious membrane fouling. Herein, a biomimetic and superwettable nanofibrous skin on an electrospun fibrous membrane via a facile strategy of synchronous electrospraying and electrospinning is created. The obtained nanofibrous skin possesses a lotus‐leaf‐like micro/nanostructured surface with intriguing superhydrophilicity and underwater superoleophobicity, which are due to the synergistic effect of the hierarchical roughness and hydrophilic polymeric matrix. The ultrathin, high porosity, sub‐micrometer porous skin layer results in the composite nanofibrous membranes exhibiting superior performances for separating both highly emulsified surfactant‐free and surfactant‐stabilized oil‐in‐water emulsions. An ultrahigh permeation flux of up to 5152 L m^?2 h^?1 with a separation efficiency of >99.93% is obtained solely under the driving of gravity (≈1 kPa), which was one order of magnitude higher than that of conventional filtration membranes with similar separation properties, showing significant applicability for energy‐saving filtration. Moreover, with the advantage of an excellent antioil fouling property, the membrane exhibits robust reusability for long‐term separation, which is promising for large‐scale oily wastewater remediation.     

Metal‐Phosphide‐Containing Porous Carbons Derived from an Ionic‐Polymer Framework and Applied as Highly Efficient Electrochemical Catalysts for Water Splitting

A novel phosphorus‐containing porous polymer is efficiently prepared from tris(4‐vinylphenyl)phosphane by radical polymerization, and it can be easily ionized to form an ionic porous polymer after treatment with hydrogen iodide. Upon ionic exchange, transition‐metal‐containing anions, such as tetrathiomolybdate (MoS₄ ^2?) and hexacyanoferrate (Fe(CN)₆ ^3?), are successfully loaded into the framework of the porous polymer to replace the original iodide anions, resulting in a polymer framework containing complex anions (termed HT‐Met, where Met = Mo or Fe). After pyrolysis under a hydrogen atmosphere, the HT‐Met materials are efficiently converted at a large scale to metal‐phosphide‐containing porous carbons (denoted as MetP@PC, where again Met = Mo or Fe). This approach provides a convenient pathway to the controlled preparation of metal‐phosphide‐loaded porous carbon composites. The MetP@PC composites exhibit superior electrocatalytic activity for the hydrogen evolution reaction (HER) under acidic conditions. In particular, MoP@PC with a low loading of 0.24 mg cm^?2 (on a glass carbon electrode) affords an iR‐corrected (where i is current and R is resistance) current density of up to 10 mA cm^?2 at 51 mV versus the reversible hydrogen electrode and a very low Tafel slope of 45 mV dec^?1, in rotating disk measurements under saturated N₂ conditions.     

Metal‐Organic Precursor–Derived Mesoporous Carbon Spheres with Homogeneously Distributed Molybdenum Carbide/Nitride Nanoparticles for Efficient Hydrogen Evolution in Alkaline Media

The generation of hydrogen through water electrolysis is considered as a sustainable approach for future fuel production. Molybdenum (Mo)‐based compounds are reported as highly active and inexpensive alternatives to platinum‐based electrocatalysts for the hydrogen evolution reaction (HER). Currently, the major challenge for Mo‐based HER electrocatalysts lies in establishing new concepts of micro‐/nanostructure design to enhance the hydrogen evolution kinetics and realizing facile, large‐scale, and green fabrication processes. Here, a fast, scalable, and eco‐friendly metal‐organic coordination precursor–assisted strategy is reported for synthesizing novel hierarchically mesoporous Mo‐based carbon electrocatalysts for efficient hydrogen production. Benefiting from homogeneously distributed Mo‐based nanocrystallites/heterojunctions and uniform mesopores, the Mo‐based mesoporous electrocatalyst shows high hydrogen evolution activity and stability with a low overpotential of 222 mV at 100 mA cm^?2 (Pt/C: 263 mV), ranging among the best non‐noble metal HER catalysts in alkaline condition. Overall, the discovery of using dopamine–molybdate coordination precursor with silica nanoparticles will not only create a new pathway for controllable synthesis of diverse kinds of micro‐/nanostructured Mo‐based catalysts, but also take a step toward the fast and scale‐up production of advanced mesoporous carbon electrodes for a broad range of applications.     

Novel Diffusion‐Barrier Materials Against Oxygen for High‐Density Dynamic Random Access Memory Capacitors

A new design concept for diffusion barriers in high‐density memory capacitors is suggested, and both RuTiN (RTN) and RuTiO (RTO) films are proposed as sacrificial oxygen diffusion barriers. The newly developed RTN and RTO barriers show a much lower sheet resistance than various other barriers, including binary and ternary nitrides (reported by others), up to 800 °C, without a large increase in the resistance. For both the Pt/RTN/TiSi_x/n⁺⁺poly‐plug/n⁺ channel layer/Si and the Pt/RTO/RTN/TiSi_x/n⁺⁺poly‐plug/n⁺ channel layer/Si contact structures, contact resistance—the most important electrical parameter for the diffusion barrier in the bottom electrode structure of capacitors—was found to be as low as 5 kohm, even after annealing up to 750 °C. When the RTN film was inserted as a glue layer between the bottom Pt electrode layer and the TiN barrier film in the chemical vapor deposited (Ba,Sr)TiO₃ (CVD–BST) simple stack‐type structure, the RTN glue layer was observed to be thermally stable to temperatures 150 °C higher than that to which the TiN glue layer is stable. Moreover, the capacitance of the physical vapor deposited (PVD)–BST simple stack‐type structure adopted TiN glue layer initially degraded after annealing at 500 °C, and, thereafter, completely failed. In the case of the RTN and RTO/RTN glue layers, however, the capacitance continuously increased up to 550 °C. Thus, the new RTN and RTO films, which act as diffusion barriers to oxygen, are very promising materials for achieving high‐density capacitors.     

Homologous CoP/NiCoP Heterostructure on N‐Doped Carbon for Highly Efficient and pH‐Universal Hydrogen Evolution Electrocatalysis

Hydrogen evolution electrocatalysts can achieve sustainable hydrogen production via electrocatalytic water splitting; however, designing highly active and stable noble‐metal‐free hydrogen evolution electrocatalysts that perform as efficiently as Pt catalysts over a wide pH range is a challenging task. Herein, a new 2D cobalt phosphide/nickelcobalt phosphide (CoP/NiCoP) hybrid nanosheet network is proposed, supported on an N‐doped carbon (NC) matrix as a highly efficient and durable pH‐universal hydrogen evolution reaction (HER) electrocatalyst. It is derived from topological transformation of corresponding layer double hydroxides and graphitic carbon nitride. This 2D CoP/NiCoP/NC catalyst exhibits versatile HER electroactivity with very low overpotentials of 75, 60, and 123 mV in 1 m KOH, 0.5 m H₂SO₄, and 1 m PBS electrolytes, respectively, delivering a current density of 10 mA cm^?2 for HER. Such impressive HER performance of the hybrid electrocatalyst is mainly attributed to the collective effects of electronic structure engineering, strong interfacial coupling between CoP and NiCoP in heterojunction, an enlarged surface area/exposed catalytic active sites due to the 2D morphology, and conductive NC support. This method is believed to provide a basis for the development of efficient 2D electrode materials with various electrochemical applications.     

Two Birds with One Stone: Metal–Organic Framework Derived Micro‐/Nanostructured Ni2P/Ni Hybrids Embedded in Porous Carbon for Electrocatalysis and Energy Storage

The construction of bifunctional electrode materials for hydrogen evolution reaction (HER) and lithium‐ion batteries (LIBs) has been a hot topic of research. Herein, metal–organic frameworks (MOFs) derived micro‐/nanostructured Ni₂P/Ni hybrids with a porous carbon coating (denoted as Ni₂P/Ni@C) are prepared using a feasible pyrolysis–phosphidation strategy. On the one hand, the optimal Ni₂P/Ni@C catalyst exhibits superior HER performance with a low overpotential of 149 mV versus a reversible hydrogen electrode (RHE) at 10 mA cm^?2 and excellent durability. The density functional theory computations verify that the strong synergistic effect between Ni₂P and Ni could optimize the electronic structure, thus rendering the enhanced electrocatalytic performance. On the other hand, the Ni₂P/Ni@C electrode displays a reversible capacity of 597 mAh g^?1 after 1000 cycles at 1000 mA g^?1 and improved rate capability as an anode for LIBs, owing to the well‐organized micro‐/nanostructure and conductive Ni core. In addition, the electrochemical reaction mechanism of the Ni₂P/Ni@C electrode upon lithiation/delithiation is investigated in detail via ex situ X‐ray powder diffraction and X‐ray photoelectron spectroscopy methods. It is expected that the facile and controllable approach can be extended to fabricate other MOF‐based metal phosphides/metal hybrids for electrochemical energy storage and conversion systems.     

A Cobalt‐Based Amorphous Bifunctional Electrocatalysts for Water‐Splitting Evolved from a Single‐Source Lazulite Cobalt Phosphate

Over the years, cobalt phosphates (amorphous or crystalline) have been projected as one of the most significant and promising classes of nonprecious catalysts and studied exclusively for the electrocatalytic and photocatalytic oxygen evolution reaction (OER). However, their successful utilization of hydrogen evolution reaction (HER) and the reaction of overall water‐splitting is rather unexplored. Herein, presented is a crystalline cobalt phosphate, Co₃(OH)₂(HPO₄)₂, structurally related to the mineral lazulite, as an efficient precatalyst for OER, HER, and water electrolysis in alkaline media. During both electrochemical OER and HER, the Co₃(OH)₂(HPO₄)₂ nanostructure was completely transformed in situ into porous amorphous CoO_x (OH) films that mediate efficient OER and HER with extremely low overpotentials of only 182 and 87 mV, respectively, at a current density of 10 mA cm^?2. When assemble as anode and cathode in a two‐electrode alkaline electrolyzer, unceasing durability over 10 days is achieved with a final cell voltage of 1.54 V, which is superior to the recently reported effective bifunctional electrocatalysts. The strategy to achieve more active sites for oxygen and hydrogen generation via in situ oxidation or reduction from a well‐defined inorganic material provides an opportunity to develop cost‐effective and efficient electrocatalysts for renewable energy technologies.