In-Situ Solid Electrolyte Interface via Dual Reaction Strategy for Highly Reversible Zinc Anode.

In-situ construction of solid electrolyte interfaces (SEI) is an effective strategy to enhance the reversibility of zinc (Zn) anodes. However, in-situ SEI to afford high reversibility under high current density conditions (≥ 20 mA cm-2) is highly desired yet extremely challenging. Herein, we propose a dual reaction strategy of spontaneous electrostatic reaction and electrochemical decomposition for the in-situ construction of SEI, which is composed of organic-rich upper layer and inorganic-rich inner layer. Particularly, in-situ SEI performs as "growth binder" at small current density and "orientation regulator" at high current density, which significantly suppresses side reactions and dendrite growth. The in-situ SEI affords the record-breaking reversibility of Zn anode under practical conditions, Zn//Zn symmetric cells can stably cycle for over 1300 h and 400 h at current densities of 50 mA cm-2 and 100 mA cm-2, respectively, showcasing an exceptional cumulative capacity of 67.5 Ah cm-2. Furthermore, the practicality of this in-situ SEI is verified in Zn//PANI pouch cells with high mass loading of 25.48 mg cm-2. This work provides a universal strategy to design advanced SEI for practical Zn-ion batteries.

Opening and Constructing Stable Lithium-ion Channels within Polymer Electrolytes.

Lithium-ion batteries play an integral role in various aspects of daily life, yet there is a pressing need to enhance their safety and cycling stability. In this study, we have successfully developed a highly secure and flexible solid-state polymer electrolyte (SPE) through the in situ polymerization of allyl acetoacetate (AAA) monomers. This SPE constructed an efficient Li+ transport channel inside and effectively improved the solid-solid interface contact of solid-state batteries to reduce interfacial impedance. Furthermore, it exhibited excellent thermal stability, an ionic conductivity of 3.82×10-4 S cm-1 at room temperature (RT), and a Li+ transport number (tLi+) of 0.66. The numerous oxygen vacancies on layered inorganic SiO2 created an excellent environment for TFSI- immobilization. Free Li+ migrated rapidly at the C=O equivalence site with the poly(allyl acetoacetate) (PAAA) matrix. Consequently, when cycled at 0.5C and RT, it displayed an initial discharge specific capacity of 140.6 mAh g-1 with a discharge specific capacity retention rate of 70 % even after 500 cycles. Similarly, when cycled at a higher rate of 5C, it demonstrated an initial discharge specific capacity of 132.3 mAh g-1 while maintaining excellent cycling stability.

In-Situ Ultrafast Construction of Zinc Tungstate Interface Layer for Highly Reversible Zinc Anodes.

Constructing artificial solid electrolyte interface on the Zn anode surface is recognized as an appealing method to inhibit zinc dendrites and side reactions, whereas the current techniques are complex and time-consuming. Here, a robust and zincophilic zinc tungstate (ZnWO4) layer has been in situ constructed on the Zn anode surface (denoted as ZWO@Zn) by an ultrafast chemical solution reaction. Comprehensive characterizations and theoretical calculations demonstrate that the ZWO layer can effectively modulate the interfacial electric field distribution and promote the Zn2+ uniform diffusion, thus facilitating the uniform Zn2+ nucleation and suppressing zinc dendrites. Besides, ZWO layer can prevent direct contact between the Zn/water and increase the hydrogen evolution reaction overpotential to eliminate side reactions. Consequently, the in situ constructed ZWO layer facilitates remarkable reversibility in the ZWO@Zn||Ti battery, achieving an impressive Coulombic efficiency of 99.36 % under 1.0 mA cm-2, unprecedented cycling lifespan exceeding 1800 h under 1.0 mA cm-2 in ZWO@Zn||ZWO@Zn battery, and a steady and reliable operation of the overall ZWO@Zn||VS2 battery. The work provides a simple, low cost, and ultrafast pathway to crafting protective layers for driving advancements in aqueous zinc-metal batteries.

Ultra-High Temperature Operated Ni-Rich Cathode Stabilized by Thermal Barrier for High-Energy Lithium-Ion Batteries.

The pursuit of high energy density batteries has expedited the fast development of Ni-rich cathodes. However, the chemo-mechanical degradation induced by local thermal accumulation and anisotropic lattice strain is posing great obstacles for its wide applications. Herein, a highly-antioxidative BaZrO3 thermal barrier engineered LiNi0.8Co0.1Mn0.1O2 cathode through an in situ construction strategy is first reported to circumvent the above issues. It is found that the Zr ions are incorporated to Ni-rich material lattice and influence on the topotactic lithiation as well as enhance the oxygen electronegativity through the rigid Zr─O bonds, which effectively alleviates the lattice strain propagation and decreases the excessive oxidization of lattice oxygen for charge compensation. More importantly, the BaZrO3 thermal barrier with an ultra-low thermal conductivity validly impedes the fast heat exchange between electrode and electrolyte to mitigate the severe surface side reactions. This helps an ultra-high mass loading Li-ion pouch cell deliver a specific energy density of 690 Wh kg-1 at active material level and an excellent capacity retention of 92.5% after 1400 cycles under 1 C at 25 °C. Tested at a high temperature of 55 °C, the pouch type full-cell also exhibits 88.7% in capacity retention after 1200 cycles.

Thermodynamic Origin-Based In Situ Electrochemical Construction of Reversible p-n Heterojunctions for Optimal Stability in Potassium Ion Storage.

Heterojunctions in electrode materials offer diverse improvements during the cycling process of energy storage devices, such as volume change buffering, accelerated ion/electron transfer, and better electrode structure integrity, however, obtaining optimal heterostructures with nanoscale domains remains challenging within constrained materials. A novel in situ electrochemical method is introduced to develop a reversible CuSe/PSe p-n heterojunction (CPS-h) from Cu3PSe4 as starting material, targeting maximum stability in potassium ion storage. The CPS-h formation is thermodynamically favorable, characterized by its superior reversibility, minimized diffusion barriers, and enhanced conversion post K+ interaction. Within CPS-h, the synergy of the intrinsic electric field and P-Se bonds enhance electrode stability, effectively countering the Se shuttling phenomenon. The specific orientation between CuSe and PSe leads to a 35° lattice mismatch generates large space at the interface, promoting efficient K ion migration. The Mott-Schottky analysis validates the consistent reversibility of CPS-h, underlining its electrochemical reliability. Notably, CPS-h demonstrates a negligible 0.005% capacity reduction over 10,000 half-cell cycles and remains stable through 2,000 and 4,000 cycles in full cells and hybrid capacitors, respectively. This study emphasizes the pivotal role of electrochemical dynamics in formulating highly stable p-n heterojunctions, representing a significant advancement in potassium-ion battery (PIB) electrode engineering.

A novel top-down strategy for in situ construction of vertically oriented hexagonal NiCr LDHs nanosheet arrays with intercalated sulfate ions on Nichrome fiber for selective solid-phase microextraction of phenolic compounds in water samples.

BACKGROUND: Phenolic compounds (PCs) are a class of polar aromatic pollutants with high toxicity in environmental water. Generally the efficient sample preparation is essential for the quantification of ultra-trace target PCs in real water sample before appropriative instrumental analysis. SPME is a convenient, solvent-free and time-saving miniaturized technique and has been recognized as a green alternative to conventional extraction techniques. In SPME, however, commercial fused-silica fibers are limited to the fragility, operation temperature, extraction capacity and selectivity as well as lifetime. Therefore, the development of new SPME fibers is always needed to overcome such limitations. RESULTS: We presented a novel top-down strategy for in situ construction of vertically oriented hexagonal sulfate intercalated NiCr layered double hydroxide nanosheet arrays (NiCr LDHs-SO4 NSAs) on the Nichrome (NiCr) substrate by hydrothermal treatment in NaOH solution containing (NH4)2S2O8. The results showed that much shorter hydrothermal time was needed for the construction of NiCr@NiCr LDHs-SO4 NSAs fiber in the presence of (NH4)2S2O8. Moreover, the unique NiCr LDHs-SO4 NSAs coating offered open access structure, and thereby more available surface area for adsorption. The resulting fiber exhibited better extraction efficiency for phenolic compounds (PCs), faster mass transfer rate, higher mechanical stability, and longer service life than original NiCr@NiCr LDHs NSs fiber and typical commercially fused-silica fibers. After optimizing conditions, the SPME-HPLC-UV method demonstrated a linear range from 0.05 µg L-1 to 200 µg L-1 with LODs of 0.015-0.156 µg L-1 (S/N = 3) and LOQs of 0.048-0.498 µg L-1 (S/N = 10), as well as good repeatability (3.06%-5.22%) and fiber-to-fiber reproducibility (4.32%-6.49%). SIGNIFICANCE: The developed SPME-HPLC-UV method with the constructed fiber was applied to the preconcentration and detection of different types of PCs in real water samples, showing satisfactory recoveries ranging from 86.20% to 107.8% with RSDs of 3.18%-6.69%. This study provides a new strategy for in situ construction of bimetallic hydroxides and their derived nanocomposite coatings on the NiCr fiber substrate in practical SPME application.

In Situ Construction of Built-In Opposite Electric Field Balanced Surface Adsorption for Hydrogen Evolution Reaction.

Achieving a balance between H-atom adsorption and binding with H2 desorption is crucial for catalyzing hydrogen evolution reaction (HER). In this study, the feasibility of designing and implementing built-in opposite electric fields (OEF) is demonstrated to enable optimal H atom adsorption and H2 desorption using the Ni3(BO3)2/Ni5P4 heterostructure as an example. Through density functional theory calculations of planar averaged potentials, it shows that opposite combinations of inward and outward electric fields can be achieved at the interface of Ni3(BO3)2/Ni5P4, leading to the optimization of the H adsorption free energy (ΔGH*) near electric neutrality (0.05 eV). Based on this OEF concept, the study experimentally validated the Ni3(BO3)2/Ni5P4 system electrochemically forming Ni3(BO3)2 through cyclic voltammetry scanning of B-doped Ni5P4. The surface of Ni3(BO3)2 undergoes reconstruction, as characterized by Grazing Incidence Wide-Angle X-ray Scattering (GIWAXS) and in situ Raman spectroscopy. The resulting catalyst exhibits excellent HER activity in alkaline media, with a low overpotential of 33 mV at 10 mA cm-2 and stability maintained for over 360 h. Therefore, the design strategy of build-in opposite electric field enables the development of high-performance HER catalysts and presents a promising approach for electrocatalyst advancement.

Achieving Dendrite-Free Solid-State Lithium-Metal Batteries via In Situ Construction of Li3P/LiCl Interfacial Layers.

Hybrid solid electrolyte (HSE) exhibits potential as a solid electrolyte due to its satisfactory Li+ conductivity, superior flexibility, and optimal interface compatibility. However, the inadequate wettability of the Li/HSE interface leads to significant contact impedance, thus fostering the formation of Li dendrites and limiting their practical applicability. Here, a straightforward strategy to enhance the interfacial wettability between Li and HSE and promote the uniform migration of Li+ by in situ construction of a multifunctional interface consisting of Li3P/LiCl (PCl@Li) was created. The Li3P component acts as a Li+ channel, banishing Li+ diffusion obstacles within the interface layer, while the electronically insulating LiCl component acts as an electron-blocking shield at the Li/HSE interface, promoting uniform Li+ deposition and preventing the formation of Li dendrites. The interface impedance of the symmetric PCl@Li|HSE|PCl@Li battery decreases markedly from 230.2 to 47.4 Ω cm-2. Additionally, the battery demonstrates superb cycling stability for over 1300 h at 0.1 mA cm-2 and maintains a minimal overpotential of 32 mV at 30 °C. The PCl@Li|HSE|LiFePO4 battery shows an initial discharge-specific capacity of 135.6 mA h g-1 at 1 C, with a notable capacity retention of 87.0% (118.0 mA h g-1) after 500 cycles. This work provides a new facile strategy for all-solid-state batteries to address interface issues between Li electrodes and HSE.

In-situ construction of fluorescent probes for hydrogen peroxide detection in mitochondria and lysosomes with on-demand modular assembling and double turn-on features.

Due to the diverse H2O2 distribution in organelles, fluorescent probes were usually required to be prepared separately, which limited the convenience and practicability. Herein, we reported a flexible strategy to in-situ construct H2O2 fluorescent probes in different organelles. A tetrazine fused probe TP was developed with rapid click reaction capacity and sensitive H2O2 response. When treated with H2O2, the turn-on fluorescence was effectively quenched by the tetrazine part. Only after click reaction with dienophiles, the fluorescence resumed. In application, cells were firstly treated with triphenylphosphorus tagged norbornene (TPP-NB) to label mitochondria, which was followed by the introduction of probe TP to trigger click reaction. The in-situ constructed probe P1 served as a local H2O2 sensor. In a similar way, probe P2 was in-situ constructed in lysosomes via probe TP and morpholine tagged norbornene (MP-NB). With this on-demand modular assembling and double turn-on features, our strategy to construct fluorescent probes presented high flexibility and anti-interference performance, which was expected to inspired more applications in biological studies.

Metal organic framework derived perovskite/spinel heterojunction as efficient bifunctional oxygen electrocatalyst for rechargeable and flexible Zn-air batteries.

Interface engineering strategy has been developed to design efficient catalysts for boosting electrocatalytic performance in past few decades. Herein, heterojunctions of PrCoO3/Co3O4 nanocages (PCO/Co3O4 NCs) with atomic-level engineered interfaces and rich oxygen vacancies are proposed for Zn-air batteries. The synthesized product shows exceptional bifunctional activity and robust stability towards oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The enhanced catalytic capacity is primary attributed to the synergistic effect of PCO/Co3O4, evidenced by the experimental results and theoretical calculations. More importantly, the PCO/Co3O4 NCs assembled liquid Zn-air battery exhibits a power density of 182 mW cm-2 and a long-term operation of 185 h. When assembled into solid-state cable type battery, this newly designed catalyst also reaches a stable open circuit voltage (1.359 V) and a peak power density of 85 mW cm-3. Our findings provide essential guidelines of engineering heterostructured electrocatalysts for future wearable electronic devices.

In Situ Construction of Thermotropic Shape Memory Polymer in Wood for Enhancing Its Dimensional Stability.

The extension of wood to a wider field has been restrained significantly due to its dimensional instability that arises from variation in moisture content, which in turn brings about the risk of cracking, warping or distortion. This work proposed a novel strategy to stabilize wood by means of the in situ construction of a thermotropic shape memory polymer (SMP) inside wood. The cross-linked copolymer network (PMP) with good shape memory behavior was first investigated based on the reaction of methyl methacrylate (MMA) and polyethylene glycol diacrylate (PEGDA) in a water/ethanol solution; then, the PMP was constructed inside wood via vacuum-pressure impregnation and in situ polymerization. The weight gain, volume increment and morphology observations clearly revealed that the PMP was mainly present in wood cell lumens, cell walls and pits. The presence of PMP significantly enhanced the dimensional stability of and reduced the cracks in wood. The desirable shape recovery abilities of PMP under heating-cooling cycles were considered to be the main reasons for wood dimensional stabilization, because it could counteract the internal stress or retard the shrinkage of cell walls once water was evaporated from the wood. This study provided a novel and reliable approach for wood modification.

In situ construction of ball-in-ball structured porous vanadium pentoxide intertwined with carbon fibers induces superior electronic/ionic transport dynamics for aqueous zinc-ion batteries.

HYPOTHESIS: Using V2O5 as an aqueous zinc-ion battery (ZIB) cathode has major drawbacks, including inferior electrode/electrolyte contact interfaces, morphological and structural deterioration, and unsatisfactory conductivity. Purposeful construction of ball-in-ball structured V2O5 with porous and void architectures wrapped with carbon fibers is expected to overcome the drawbacks, thus bringing the electrochemical performance of V2O5 into full play. EXPERIMENTS: In situ construction of ball-in-ball structured porous V2O5 wrapped by intertwined carbon fibers (V2O5@void@V2O5@CFs) is implemented through a simple combined hydrothermal and calcination route. A combination of in/ex situ analytical methods and density functional theoretical calculations are performed to clarify the energy storage mechanism of the material for aqueous ZIBs. FINDINGS: The reversible reaction to generate ZnxV2O5·nH2O executes during the zinc ion insertion/extraction procedure in V2O5@void@V2O5@CFs. Benefitting from the synergistic effect of the porous ball-in-ball structure with void space and the wrapped CFs, the material exhibits boosted specific capacity (455 mAh g-1 after 100 cycles and 149 mAh g-1 after 2000 cycles at 4 and 25 A g-1, respectively), cyclic stability, rate ability and energy density (355 Wh kg-1 at 739 W kg-1) when used for aqueous ZIBs due to improved capacitive contribution, fast zinc ion transport dynamics, and enhanced conductivity.

Functionalization of cellulose fibers alongside growth of 2D LDH platelets through urea hydrolysis inspired Taro wettability.

Here, Cotton fabric was functionalized via hybrid coating including 2D MgAl LDH (layered double hydroxide) and SA (stearic acid). The urea hydrolysis was employed for construction of vertically aligned LDH on surface of cellulose fibers under hydrothermal condition. The in situ formation mechanism of LDH on cotton surface was nucleation, growth, and interaction with activated cellulose chains. The partial cellulose ionization in the alkaline solution led to nucleophilic behavior towards electron deficient atom. The effect of different ageing, synthesis temperature, and amount of SA were investigated and optimized at 100 °C for 24 h with 0.05 M. The superhydrophobic surface architecture of treated cotton with hierarchical micro/nanostructure was inspired from the Taro leaf structure with continuous contact line presented WCA of 154 ° and CAH of 9 °. The Cotton@LDH@SA exhibited efficient oil/water separation after several washes (>90%) with good stain resistant. Also, the physico-mechanical properties were studied.

Tetragonal/orthorhombic-bismuth tungstate homojunction formed through in situ bismuth induced phase transformation as highly efficient photocatalyst for pollutant degradation.

Tetragonal/orthorhombic-bismuth tungstate (t/o-Bi2WO6) homojunctions of high photocatalytic efficiencies were fabricated through a novel in situ Bi induced phase transformation. The photocatalytic efficiencies of t-Bi2WO6 were greatly enhanced via formation of the homojunction. Photocatalytic degradation of rhodamine B (RhB), a recalcitrant organic pollutant, under simulated sunlight illumination was investigated as a demonstration for the efficiency enhancement. A 6.22 folds improvement was achieved with formation of the homojunction in terms of reaction rate constants. The homojunction catalyst was demonstrated to be photocatalytically stable over a five cycles operation. The t/o-Bi2WO6 homojunction enhances separation and utilization efficiency of photo-generated charge carriers and thus greatly boosts the catalytic efficiency. Trapping tests and electron spin resonance spectroscopy were conducted to reveal that singlet oxygen (1O2), hole (h+), electrons (e-), and superoxide anion radical (O2-) are the main working reactive species for RhB degradation. Density functional theory (DFT) calculations were performed to prove the feasibility of Bi induced phase transformation of t-Bi2WO6 to o-Bi2WO6. The present development offers a new design route for high efficiency photocatalysts for water pollution control.

In situ constructed honeycomb-like NiFe2O4@Ni@C composites as efficient electromagnetic wave absorber.

Rational excogitation of microstructure and chemical constituents is a superior means of constructing electromagnetic wave (EMW) absorption materials with high performance. In this study, a kind of honeycomb-like NiFe2O4@Ni@C composite is prepared via an uncomplicated polymerization, pyrolysis and etching. Porous structure and internal cavity of NiFe2O4@Ni@C contribute to the numerous reflection and scattering of EMW. The strong ferromagnetic resonance of NiFe2O4 core and the multiple relaxation processes of porous carbon shell strongly promote the EMW loss. Additionally, the synergistic effect can improve impedance matching. The results demonstrate that the minimum reflection loss (RL) of honeycomb-like NiFe2O4@Ni@C composites is -65.33 dB at 13.63 GHz. The effective absorption bandwidth (EAB) is 3.68 GHz when the matching thickness is 4.95 mm. The mechanism of EMW dissipation of the honeycomb-like NiFe2O4@Ni@C composites is attributed to multiple reflections and scattering, conductive loss, interfacial polarization and ferromagnetism resonance. This work provides a tactic for the excogitation and synthesis of a low cost, light weight and efficient EMW absorber.

In-situ construction of 3D hetero-structured sulfur-doped nanoflower-like FeNi LDH decorated with NiCo Prussian blue analogue cubes as efficient electrocatalysts for boosting oxygen evolution reaction.

At present, it is urgent for us to develop non-noble metal-based catalysts with abundant reserves and high efficiency towards oxygen evolution reaction (OER) in water electrolysis devices. Herein, cubic NiCo-Prussian blue analogue (PBA)/ flower-like FeNi layered double hydroxide (LDH) heterostructure was facilely in-situ formed on porous nickel foam (NF) via hydrothermal strategy coupled by subsequent sulfurizing treatment (named as S-FeNi LDH@PBA/NF), showing largely facilitated electron transfer over homogeneous counterpart. Also, we investigated the effects of different Fe/Ni feeding ratios on their catalytic properties in some detail. The as-prepared S-FeNi LDH@PBA/NF demonstrated the superior OER activity (e.g. only 243 mV of overpotential required for 50 mA cm-2) and stability. Accordingly, using the catalyst as anode, the home-assembled S-FeNi LDH@PBA/NF//Pt/C/NF electrolyzer exhibited small Tafel slope (83.1 mV dec-1) and ultra-stability, showing the potential feasibility in practical water electrolysis. This strategy provides a hopeful model to enhance the OER performance by effectively constructing advanced catalyst with promising heterostructure and optimal electronic structure.

In Situ Construction of Flexible VNi Redox Centers over Ni-Based MOF Nanosheet Arrays for Electrochemical Water Oxidation.

Atomic-level design and construction of synergistic active centers are central to develop advanced oxygen electrocatalysts toward efficient energy conversion. Herein, an in situ construction strategy to introduce flexible redox sites of VNi centers onto Ni-based metal-organic framework (MOF) nanosheet arrays (NiV-MOF NAs) as a promising oxygen electrocatalyst is developed. The abundant redox VNi centers with flexible metal valence states of V+3/+4/+5 and Ni+3/+2 enable NiV-MOF NAs excellent oxygen evolution reaction (OER) activity and a long-term stability under high current densities, achieving current densities of 10 and 100 mA cm-2 at recorded overpotentials of 189 and 290 mV, respectively, and showing ignorable decay of initial activity at 100 mA cm-2 after 100 h OER operation. Operando synchrotron radiation Fourier transform infrared combined with quasi in situ X-ray absorption fine structure spectroscopies reveal at atomic level that the flexible V sites can continuously accept electrons from adjacent active Ni sites to accelerate OER kinetics for NiV-MOF NAs during the reaction process, accompanied by a self-optimized structural distortion of VO6 octahedron for promoting the electrochemical stability.

Lab-on-fiber sensing system based on responsive Fabry-Perot optical resonance cavities prepared throughin situconstruction strategy.

For decades, lab-on-fiber (LOF) sensing systems have become an emerging optical sensing platform due to the features of small size and light weight. Herein, a simple and efficientin situconstruction strategy was reported for the preparation of LOF sensing platform based on the integration of responsive Fabry-Perot optical resonance cavity on optical fibers. The responsive Fabry-Perot optical resonance cavity with thermal poly(N-isopropylacrylamide) polymer brush layer sandwiched by two silver layers was constructed on the end surface of the optical fiber through combiningin situsurface-initiated polymerization and metal film deposition techniques. Owing to the thermo-responsiveness of the intermediate layer, the as-prepared LOF sensing system shows a sensitive response towards the environmental temperature. Importantly, the as-prepared LOF sensing system also possesses excellent repeatability and rapid response rate. Together with the features of high sensitivity, excellent repeatability and rapid response rate, we believe such LOF sensing system will provide a foundation for the future applications of medical diagnosis,in vivodetection and public security.

Rational Construction of a N, F Co-doped Mesoporous Cobalt Phosphate with Rich-Oxygen Vacancies for Oxygen Evolution Reaction and Supercapacitors.

Transition-metal phosphates have been widely applied as promising candidates for electrochemical energy storage and conversion. In this study, we report a simple method to prepare a N, F co-doped mesoporous cobalt phosphate with rich-oxygen vacancies by in-situ pyrolysis of a Co-phosphate precursor with NH4 + cations and F- anions. Due to this heteroatom doping, it could achieve a current density of 10 mA/cm2 at lower overpotential of 276 mV and smaller Tafel slope of 57.11 mV dec-1 on glassy carbon. Moreover, it could keep 92 % of initial current density for 35 h, indicating it has an excellent stability and durability. Furthermore, the optimal material applied in supercapacitor displays specific capacitance of 206.3 F g-1 at 1 A ⋅ g-1 and maintains cycling stability with 80 % after 3000 cycles. The excellent electrochemical properties should be attributed to N, F co-doping into this Co-based phosphate, which effectively modulates its electronic structure. In addition, its amorphous structure provides more active sites; moreover, its mesoporous structure should be beneficial to mass transfer and electrolyte diffusion.

In Situ Growth of Ultrafine Pt Nanoparticles onto Hierarchical Co3 O4 Nanosheet-Assembled Microflowers for Efficient Electrocatalytic Hydrogen Evolution.

The development of Pt-based electrocatalysts with high Pt utilization efficiency toward the hydrogen evolution reaction (HER) is of great significance for the future sustainable hydrogen economy. For rational design of high-performance HER electrocatalyst, the simultaneous consideration of both thermodynamic and kinetic aspects remains greatly challenging. Herein, a simple template-derived strategy is demonstrated for the in situ growth of ultrafine Pt nanoparticles onto Co3 O4 nanosheet-assembled microflowers (abbreviated as Pt/Co3 O4 microflowers hereafter) by using the pre-fabricated PtCo-based Hofmann coordination polymer as reactive templates. The elaborate preparation of such intriguing hierarchical architecture with well-dispersed tiny Pt nanoparticles, abundant metal/oxide heterointerfaces and open configuration endows the formed Pt/Co3 O4 microflowers with high Pt utilization efficiency, rich active sites, lowered energy barrier for water dissociation and expedited reaction kinetics. Consequently, the Pt/Co3 O4 microflowers exhibit superior HER activity with a relatively low overpotential of 34 mV to deliver a current density of 10 mA cm-2 , small Tafel slope (34 mV dec-1 ) and outstanding electrochemical stability, representing an attractive electrocatalyst for practical water splitting. What's more, our concept of in situ construction of metal/oxide heterointerfaces may provide a new opportunity to design high-performance electrocatalysts for a variety of applications.