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A novel and convenient approach to the synthesis of various tertiary phosphines via a copper-catalyzed cross-coupling of (hetero)aromatic bromide with secondary phosphines has been developed. The reaction employs cheap copper as the catalyst, 2,6-bis(N-methylaminomethyl)pyridine (L4) as a perfect ligand and KOtBu as a base; all reactions are carried out under argon atmosphere. A variety of sterically hindered and/or functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields. Moreover, ten new tertiary phosphines were first reported in this process. [ABSTRACT FROM AUTHOR]

Hierarchical FeP nanoarray films composed of FeP nanopetals were successfully synthesized via a bio-inspired hydrothermal route followed by phosphorization. Glycerol, as a crystal growth modifier, plays a significant role in controlling the morphology and structure of the FeO(OH) precursor during the biomineralization process, while the following transfer and pseudomorphic transformation of the FeO(OH) film successfully give rise to the FeP array film. The as-prepared FeP film electrodes exhibit excellent hydrogen evolution reaction (HER) performance over a wide pH range. Theoretical calculations reveal that the mixed P/Fe termination in the FeP film is responsible for the high catalytic activity of the nanostructured electrodes. This new insight will promote further explorations of efficient metal phosphoride-based catalysts for the HER. More importantly, this study bridges the gap between biological and inorganic self-assembling nanosystems and may open up a new avenue for the preparation of functional nanostructures with application in energy devices. [ABSTRACT FROM AUTHOR]

Owing to the metalloid characteristic and superior electrical conductivity, the metal phosphides have received increasing interests in energy storage systems. Here, x rGO/Ni 2 P composites are successfully synthesized via an In-situ phosphorization process with GO/Ni-MOF as precursors. Compared to pure Ni 2 P, the x rGO/Ni 2 P composites appear enhanced electrochemical properties in terms of the specific capacitance and cycling performance as electrodes for supercapacitors. Especially, the 2rGO/Ni 2 P electrode shows a highest specific capacitance of 890 F g −1 at 1 A g −1 among the obtained composites. The enhancement can be attributed to the inherited structure from Ni-MOF and the well assembled of rGO and Ni 2 P through the In-situ conversion process. Moreover, when applied as positive electrode in a hybrid supercapacitor, an energy density of 35.9 W h kg −1 at a power density of 752 W kg −1 has been achieved. This work provides an In-situ conversion strategy for the synthesis of rGO/Ni 2 P composite which might be a promising electrode material for SCs. [ABSTRACT FROM AUTHOR]

Although great advances have been achieved in the field of electrocatalysis, the design of highly efficient and stable earth-abundant electrocatalysts for overall water splitting remains a significant challenge. Herein, we have successfully developed cost-efficient three dimensional (3D) highly open hierarchical catalysts with cobalt-molybdenum nanosheet arrays on nickel foam (NF) (denoted as CoMoO NSs@NF) and CoMoP NSs@NF via phosphorization for efficient overall water splitting. The optimized Co 5 Mo 1.0 O NSs@NF exhibits excellent OER activity with low overpotentials of 270 mV at 10 mA cm −2 and superior stability after 140 h and the optimized Co 5 Mo 1.0 P NSs@NF shows excellent HER activity with low overpotential of 173 mV at 10 mA cm −2 and superior stability after 1000 CV cycles. In addition to the enhanced electron migration and mass transfer benefited from the 3D structure, the XPS analysis shows that Mo plays a vital role on modulating the number of active sites on the surface, leading to the electrocatalytic enhancement. Significantly, the Co 5 Mo 1.0 O NSs@NF//Co 5 Mo 1.0 P NSs@NF couple showed highly efficient overall water electrolysis with a low potential of 1.68 V at 10 mA cm −2 in an alkaline electrolyzer as well as excellent stability after long-term water splitting, holding great potential for practical overall water splitting electrocatalysis. [ABSTRACT FROM AUTHOR]

The phosphorized radial microspheres of Ni-Co-O on a porous Ti plate (Ni-Co-O/Ti) were fabricated for the electrocatalysis of hydrogen evolution reaction (HER). They are characterized by SEM, TEM, XRD, XPS and BET. The Ni-Co-P/Ti exhibited the low onset potential of −100 mV, achieving the current densities of 10 and 50 mA/cm 2 at the overpotentials of 20 and 80 mV, respectively. The Tafel slope is approximately 43 mV/dec, which is close to that of commercial Pt catalyst and lower than many previous reports. On the other hand, the Ni-Co-O/Ti exhibited high electrocatalytic oxidation of glucose with a relatively low onset potential at 0.29 V, where glucose was introduced to decrease the cell potential of water splitting. [ABSTRACT FROM AUTHOR]

Hitherto, WP has been used as hydrogen evolution reaction (HER) catalyst. However, its activity and complexity of nanostructure synthesis greatly limit applications in hydrogen production. Therefore, in this work, the coral-like WP nanorod arrays propagated on W foils (C-WP/W) are synthesized through an in situ oxidation and phosphorization route. The obtained 3D C-WP/W catalysis system can directly work as hydrogen evolution reaction (HER) electrode, and exhibits excellent activity and stability in either acid or alkaline media. It only requires a small overpotential of 109 and 133 mV at 10 mA/cm 2 , and 189 and 206 mV at 100 mA/cm 2 in 0.5 M H 2 SO 4 and 1.0 M KOH, respectively, which is the best HER catalyst ever reported among pure tungsten phosphide materials. This study paves the way for integrations of 3D HER electrodes with low-cost, high performance and for efficient applications under complicated conditions. [ABSTRACT FROM AUTHOR]

A NiFe-based integrated electrode is fabricated by the spontaneous galvanic replacement reaction on an iron foam. Driven by the different electrochemical potentials between Ni and Fe, the dissolution of surface Fe occurs with electroless plating of Ni on iron foam with no need to access instrumentation and input energy. A facile cyclic voltammetry treatment is subsequently applied to convert the metallic NiFe to NiFeO x. A series of analytical methods indicates formation of a NiFeO x film of nanosheets on the iron foam surface. This hierarchically structured three dimensional electrode displays high activity and durability against water oxidation. In 1 m KOH, a current density of 1000 mA cm−2 is achieved at an overpotential of only 300 mV. This method is readily extended to fabricate CoFe or NiCoFe-based integrated electrodes for water oxidation. Phosphorization of the bimetallic oxide (NiFeO x) generates the bimetallic phosphide (NiFe-P), which can act as an excellent electrocatalyst for hydrogen production in 1 m KOH. An alkaline electrolyzer is constructed using NiFeO x and NiFe-P coated iron foams as anode and cathode, which can realize overall water splitting with a current density of 100 mA cm−2 at an overpotential of 630 mV. [ABSTRACT FROM AUTHOR]

[Display omitted] • Phosphorization coupled activation strategy enhances performance to 639%. • Phosphate leaching triggers reconstruction to form (Ni,Co)OOH nanosheets. • Activation-derived electrode has high mass loading and capacitance (10.86 F cm−2). • Quasi-solid-state supercapacitor shows superior volumetric energy/power density. It is crucial for next-generation energy storage devices to develop high performance electrode materials. For the real commercial application of supercapacitors, high mass loading, and high performance are expected at the same time. Herein, NiCo 2 O 4 is directly grown on nickel foam (NiCo 2 O 4 /NF) via simple drying and annealing process. Then phosphorization and electrochemical activation (A-P-NiCo 2 O 4 /NF) were carried out, and the phase transformation and reaction mechanism were investigated. The etching of PO 4 3- during activation generates unsaturated sites that trigger phase evolution behavior, resulting in self-optimization of the electrode and formation of polycrystalline, defect-rich nanostructures ((Ni,Co)OOH nanosheets), which greatly enhances the electrochemical activity. The electrochemical evaluation showed that the areal specific capacitance of A-P-NiCo 2 O 4 /NF with a high mass loading of 11.2 mg cm−2 was significantly enhanced (≈639%, from 1.7 to 10.86 F cm−2 at 1 mA cm−2). Meanwhile, the assembled quasi-solid-state A-P-NiCo 2 O 4 /NF//activated iron foam device exhibits a superior volumetric energy density of 10.68 mWh cm−3 at the power density of 14.17 mW cm−3. This work reveals the mechanism of phosphorus functionalization to enhance performance and provides a simple coupling approach to realize the enhancement in the energy storage of commercial-level bimetallic nickel–cobalt-based materials. [ABSTRACT FROM AUTHOR]

The metal-organic frameworks (MOFs)/derivates emerged as promising catalysts for hydrogen generation from electrolyzing water, however, further improvements in the activities are still awaited. Herein, bimetallic MOFs and the derivates were developed for catalyzing the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) by regulating the morphology, and activity of the intermediates. We demonstrated the activity and morphology of the catalysts strongly correlated with the atomic ratio of Ni and Co in bimetallic MOFs. The hierarchical Ni 0.1 Co 0.9 -MOF delivered a relatively low overpotential of 384 mV to afford 100 mA/cm2 for OER, but a high overpotential of 512 mV for HER. While the phosphide Ni 0.1 Co 0.9 P only needed an overpotential of 276 mV to deliver 100 mA/cm2 for HER. And we discussed the roles of bimetallic sites and phosphorous in OER and HER in depth. More importantly the Ni 0.1 Co 0.9 -MOF and Ni 0.1 Co 0.9 P were integrated to drive the overall water splitting, at a current density of 10 mA/cm2, the overpotential value is 500 mV. This work provided insights into the exploration of efficient MOFs/derivates catalysts and shed new light on the novel combination for water electrolysis. [Display omitted] • The hierarchical nanoflower morphology is elaborately fabricated. • The OER activity highly depends on the metallic atomic ratio in NiCo-MOF. • Ni 0.1 Co 0.9 -MOF performs the most superior OER performance. • Boosted HER performance is achieved by phosphorization (Ni 0.1 Co 0.9 P). • Paring Ni 0.1 Co 0.9 -MOF and Ni 0.1 Co 0.9 P generate excellent water electrolysis. [ABSTRACT FROM AUTHOR]

Controllable synthesis of mesoporous conductive metal phosphide nanowire arrays is critical for developing highly-active electrodes of alkaline batteries. Herein we develop a simple combined strategy for rational synthesis of mesoporous Co 2 P nanowire arrays by hydrothermal-phosphorization method. Free-standing mesoporous Co 2 P nanowires consisting of interconnected nanoparticles of 10–20 nm grow vertically to the substrate forming arrays. High electrical conductivity and large porosity are obtained in the arrays architecture. When characterized as the cathode of high-rate alkaline batteries, the designed Co 2 P nanowire arrays are proven with good electrochemical performance with a large capacity (133 mAh g −1 at 1 A g −1 ), stable cycling life with a capacity retention of almost 100% after 5000 cycles at 10 A g −1 owing to the mesoporous nanowire structure with short ion/electron transport path. Our synthetic approach can be useful for construction of other porous metal phosphide arrays for energy storage and conversion. [ABSTRACT FROM AUTHOR]

• Triphenylphosphine (PPh3) was used for the phosphorization of g-C 3 N 4. • g-C 3 N 4 (PPh3) showed extended light absorption and promoted charge separation. • g-C 3 N 4 (PPh3) exhibited higher photocatalytic activity than g-C 3 N 4. It is an effective strategy to regulate the structure of photocatalysts for enhanced photocatalytic hydrogen evolution. In this work, a facile method was developed to introduce P atoms into g-C 3 N 4 via the thermal calcination treatment. In contrast to pristine g-C 3 N 4 , the obtained P-CN(PPh3) exhibited a negative shift of conduction band edge with enhanced light absorption after the introduction of P atoms into g-C 3 N 4 , thus benefiting the photocatalytic hydrogen evolution. Moreover, the introduction of P element in g-C 3 N 4 can also improve the charge separation during the photocatalytic hydrogen reaction, significantly accelerating the photocatalytic hydrogen production rate of P-CN(PPh3). [ABSTRACT FROM AUTHOR]

• Stainless steel mess with a three-dimensional network structure substrate to grow NiCoP-CoP electroactive catalyst. • NiCoP@SSM electrocatalyst reveals an excellent performance and stability towards hydrogen evolution reaction. • Synergetic effect between Pδ− with a high affinity towards proton-acceptor, and Coδ+/ Niδ+ as hydride-acceptor. The stainless steel mesh (SSM) has received remarkable attention for hydrogen and oxygen evolution reactions. It was demonstrated that the SSM exhibits admirable performance towards oxygen evolution reaction (OER) electrocatalysis, while its catalytic activity for hydrogen evolution reaction (HER) remains quite low. This obstructs the utilization of SSM-based catalysts for sustainable complete water electrolysis. In this study, a facile hydrothermal route followed by a phosphorization process was adopted to transform commercially available SSM materials into high-performance and stable electrocatalysts for alkaline HER. We report an interconnected NiCoP-CoP sponge-like structure on SSM substrate without polymer binder. Benefiting from the 3D construction with high exposed surface area, close contact between electroactive species and conductive surface, and facilitated infiltration of electrolyte, the as-prepared NiCoP@SSM electrocatalyst brought an improved catalytic activity for HER, required a low overpotential of 138 mV to derive a current density of 10 mAcm−2 in 1.0 M KOH aqueous solution. The high performance of the NiCoP@SSM catalyst has also unveiled fast reaction kinetics (presents a small Tafel slope of 74 mV/dec), a relatively large electrochemical active surface area (ECSA), and small charge transfer resistance. Furthermore, the NiCoP@SSM electrode also presented excellent stability during long-term measurements, making it one of the most encouraging HER electrodes to date. This research study paves the way for the development of HER-active electrocatalysts made from SSMs that are commercially available, low-cost, and highly active. [Display omitted] [ABSTRACT FROM AUTHOR]

Transition-metal oxides as the pseudocapacitive material have been increasingly investigated due to their high theoretical specific capacitance for supercapacitors (SCs). However, restricted to lack of active sites and poor conductivity, they usually display limited experimental capacitance, barely satisfying high energy density of SCs. Herein, we describe phosphorus functionalized low-crystallinity Co 3 O 4 and Fe 2 O 3 nanorod arrays on carbon cloth (Co 3 O 4 -P and Fe 2 O 3 -P), which can respectively behave as the flexible 3D cathode and anode for SCs. The formed phosphide on the surface of metal oxide provides the enhancement of electron transfer and the reduction of ions diffusion pathway. The optimized Co 3 O 4 -P 1.0 h cathode and Fe 2 O 3 -P 1.0 h anode deliver a high capacitance of 1180 and 477 mF cm−2, respectively. The asymmetric supercapacitor Co 3 O 4 -P//Fe 2 O 3 -P has been verified with an operating voltage of 1.5 V and stability over 5000 cycles and delivers an energy density of 73.6 μWh cm−2 at a power density of 0.38 mW cm−2. The phosphorus activation is expected to be widely applicable for the fabrication of porous and low-crystalline transition-metal oxide, thus opening up new avenues for energy storage. [Display omitted] • Low-crystalline Co 3 O 4 -P and Fe 2 O 3 -P nanoarrays were fabricated by incomplete phosphorization treatment. • Structure defect of metal oxides by rational phosphorization favors electrolyte ions transport. • The formation of phosphide in bulk phase accelerates electrons transfer of electrode. • Co 3 O 4 -P//Fe 2 O 3 -P assembled ASC delivered high energy density and superior cycling stability. [ABSTRACT FROM AUTHOR]

In this study, a general and effective phosphorization strategy is successfully demonstrated to enhance supercapacitor performance of various transition metals oxide or hydroxide, such as Ni(OH)2, Co(OH)2, MnO2, and Fe2O3. For example, a 3D networked Ni2P nanosheets array via a facile phosphorization reaction of Ni(OH)2 nanosheets is grown on the surface of a Ni foam. The Ni foam-supported Ni2P nanosheet (Ni2P NS/NF) electrode shows a remarkable specific capacitance of 2141 F g−1 at a scan rate of 50 mV s−1 and remains as high as 1109 F g−1 even at the current density of 83.3 A g−1. The specific capacitance is much larger than those of Ni(OH)2 NS/NF (747 F g−1 at 50 mV s−1). Furthermore, the electrode retains a high specific capacitance of 1437 F g−1 even after 5000 cycles at a current density of 10 A g−1, in sharp contrast with only 403 F g−1 of Ni(OH)2 NS/NF at the same current density. The similar enhanced performance is observed for Ni2P powder, which eliminates the influence of nickel foam. The enhanced supercapacitor performances are attributed to the 3D porous nanosheets network, enhanced conductivity, and two active components of Ni2+ and Pδ− with rich valences of Ni2P. [ABSTRACT FROM AUTHOR]

Rational design of bifunctional two-dimensional (2D) heterostructures with excellent activity and durability remains a great challenge for electrocatalytic water splitting. Herein, we propose a topochemical domain engineering to realize 2D mosaic heterostructures with ultrafine phosphide nanodomains highly dispersed on the surface of Ru doped CoMoO 4 nanosheets (denoted as Ru-CMOP), which are vertically interconnected on the conductive skeleton assembling a 3D array structure. The as-prepared Ru-CMOP electrocatalyst exhibits excellent activity and long-term stability with the overpotentials of 114 and 286 mV at 100 mA cm−2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1.0 M KOH solution, respectively, outperforming most reported metal phosphide-based bifunctional heterostructures. Moreover, an assembled electrolyzer using the Ru-CMOP as anode and cathode simultaneously delivers cell voltages of 1.697 V and 1.828 V to achieve 100 mA cm−2 and 500 mA cm−2, respectively, with outstanding durability at 250 mA cm−2 for 120 h. Density functional theory calculations and experimental results indicate that the strongly coupled heterointerfaces with built-in electric field can facilitate electron transfer while multi-porous nanosheet arrays contribute to active sites exposure and mass/gas transport, thereby synergistically accelerating the reaction kinetics. Additionally, combining with a commercial silicon photovoltaic solar cell, the electrolyzer can be efficiently and robustly established, demonstrating the great potential for practical photovoltaic-electrolysis applications. [Display omitted] • 2D mosaic heterostructures are prepared by topochemical domain engineering. • The Ru-CMOP exhibits outstanding activity and stability for HER and OER in alkaline media. • The rich heterointerfaces optimize the electronic configuration, indicated by DFT calculations. • A solar-cell-driven overall water-splitting device is efficiently constructed. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel hierarchical CdS-DETA@CoP composite is first synthesized. • CdS-DETA@CoP exhibits excellent visible-light-driven photocatalytic performance. • The synergistic effect can boost the separation efficiency of electron-hole pairs. The photolysis of water using photocatalysts under sunlight irradiation for hydrogen generation reaction is an efficient strategy to solve energy and environmental issues. Herein, a novel hierarchical CdS-DETA@CoP composite was fabricated and applied to visible-light-driven photocatalytic water splitting for generating H 2. To achieve this goal, we first prepared a 3D hierarchical CoP co-catalyst via direct phosphatization of the ZIF-67 precursor. Then, two-dimensional (2D) CdS-DETA nanosheets were in situ grown on the surface of hierarchical CoP through a facile water bath method, obtaining a CdS-DETA@CoP composite with a high surface area. The CdS-DETA@CoP composite with 20 wt% CoP exhibits a maximum photocatalytic H 2 evolution rate of 48.76 mmol g–1h−1 under visible light irradiation with lactic acid as the sacrificial reagent, which is 46.4 times as high as CdS-DETA. The synergistic effect between CdS-DETA and CoP induced remarkable ability of light-harvesting and efficient separation of photogenerated electron-hole pairs, thus profoundly promoting the activity and stability. The excellent activity is also closely related to the better dispersion of CdS-DETA on the surface of hierarchical CoP co-catalyst. [ABSTRACT FROM AUTHOR]

The Ti-6Al-4V alloy was treated in concentrated phosphoric acid solution and by powder blasting, respectively, subsequently coated by silica using sol-gel dip-coating technique. A barrier layer of titanium pyrophosphate (TiPO) was synthesized at the Ti-6Al-4V substrate surface after the heat treatment. XRD and SEM/EDS analysis revealed that an amorphous silica coating was formed on the alloy. The isothermal and cyclic oxidation behavior of the treated alloy with silica coating and the corresponding bare alloy was investigated at 600 °C in static air to investigate the synergetic effect of the SiO coating and surface treatment on the oxidation resistance of the alloy by thermogravimetry. The average parabolic rate constants of the treated specimens with silica coating were greatly reduced. The stratified oxide layer formed on the bare alloy, while thinner oxide layer formed on the treated alloys with silica coating. The oxidation resistance of the present alloy was improved. The effect of silica coating on the microhardness of the substrate was investigated. [ABSTRACT FROM AUTHOR]

Abstract: A highly loaded P-Ni/SiO2 catalyst with the high active nickel surface area was prepared by the co-precipitation method with an n-butanol drying process. Phosphorization of this catalyst with 10%PH3 in H2 at 423K resulted in a supported Ni2P catalyst P-Ni2P/SiO2. This catalyst showed the high surface area (152m2/g) with highly and uniformly dispersed Ni2P nano-particles (∼4.2nm). Thus, it possessed the high density of active sites of Ni2P as titrated by the adsorption of CO (263μmol/g). Accordingly, it exhibited excellent performance for the hydrodesulfurization of dibenzothiophene, hydrodenitrogenation of quinoline and hydrogenation of tetralin in a model diesel. [Copyright &y& Elsevier]

Photocatalytic pure water splitting using particulate photocatalyst is usually restricted by the extremely slow reaction kinetics. Herein, we demonstrated a novel Z-scheme heterojunction, composed of a phosphatized p-type gallium indium zinc oxynitride (GIZON-P) and a n-type g-C 3 N 4 (CN). Results show that phosphorization could reduce hole concentration within p-type GIZON, resulting in the transition of Z-scheme band structure into type-Ⅱ style. This transformation leads to a completely changed reaction mechanism, i.e., from a two-electron H 2 /H 2 O 2 production to a four-electron H 2 /O 2 generation. Although this four-electron pathway is dynamically unfavorable, the rapid charge separation by the type-II band arrangement together with thin InP layer at the surface of GIZON-P could remarkably accelerate the rate-limited O 2 -evolution process. The phosphatized composite presents an excellent photocatalytic performance, with a H 2 /O 2 rate of 1340/643 μmol h g. The gained quantum yield of 12.6% at 430 nm is among the best results in photocatalytic pure water splitting. [Display omitted] • A heterojunction photocatalyst composed of GaInZnON and g-C 3 N 4 is prepared. • Phosphorization enables transition of Z-scheme band behavior into a type-Ⅱ style. • Photocatalytic water splitting switches from two-electron to four-electron pathway. • Phosphorization can remarkably accelerate the rate-limited O 2 -evolution process. • Photocatalytic overall water splitting with an AQE of 12.6% is achieved. [ABSTRACT FROM AUTHOR]

[Display omitted] • Sn/SnP 2 O 7 composite was synthesized by anodization and phosphorization. • The material was comprised of Sn nanoparticles embedded in the SnP 2 O 7 matrix. • Sn/SnP 2 O 7 exhibits excellent storage for Li and Na ions compared to Sn/SnO x. • Reversible capacities with a 100 % efficiency were achieved up to 1000 cycles. Two types of Sn-based nanostructured materials have been investigated as anodes in lithium-ion batteries (LIB) and sodium-ion batteries (SIB). Firstly, nanostructured Sn/SnO x powders were synthesized by one-step anodic oxidation of Sn foil in an alkaline electrolyte followed by mechanical separation of the anodic film from the remaining substrate. Secondly, as-anodized powders were converted for the first time to tin oxyphosphate (Sn/SnP 2 O 7) hybrid via a simple phosphorization with red phosphorous at 500 °C. The XRD and HR-TEM analyses confirmed that the hybrid was comprised of Sn nanoparticles embedded in the SnP 2 O 7 matrix. When used as anode materials, the Sn/SnP 2 O 7 exhibits excellent storage performance for lithium and sodium ions compared to Sn/SnO x that can be attributed to the metal/matrix structure which is not only conducive to the electron transport but also can facilitate the accommodation of volume changes during intercalation/deintercalation processes. A stable reversible capacity with an excellent coulombic efficiency of nearly 100% at different current densities even up to 1000 cycles was achieved for the Sn/SnP 2 O 7 anode in LIB. [ABSTRACT FROM AUTHOR]

B-type carbonate apatite (CO3Ap) block may be an ideal artificial bone substitute because it is closer in chemical composition to bone mineral. In the present study, the feasibility to fabricate CO3Ap blocks was investigated using compositional transformation, which was based on the dissolution-precipitation reaction of a gypsum-calcite composite with free-molding behavior. For the compositional change, or phosphorization, gypsum-calcite composites of varying CaCO3 contents were immersed in 1 mol/L (NH4)3PO4 aqueous solution at 100°C for 24 hours. No macroscopic changes were found after the treatment, whereas microscopic change was observed at SEM level. X-ray diffraction, Fourier transform infrared spectroscopy and CHN analysis indicated that the composites were B-type CO3Ap containing approximately 6-7 wt% of CO3, a value similar to that of biological bone apatite. Diametral tensile strength of the CO3Ap block was approximately 1-3 MPa. Based on the results obtained, it was therefore concluded that gypsum-calcite was a good candidate for the fabrication of CO3Ap blocks, coupled with the advantage that the composite can be molded to any shape by virtue of the setting property of gypsum. [ABSTRACT FROM AUTHOR]

[Display omitted] • The CoMoP-rGO/CNT was synthesized by hydrothermal and phosphating. • The three-dimensional rGO/CNTs can improve the conductivity of substrate materials. • The vertical open structure of CoMoP nanosheet arrays facilitates mass transfer. • The CoMoP-rGO/CNT exhibits HER activity and durability in pH-universal. Although great progress has been made in the area of electrocatalysis, the design of earth-rich and efficient electrocatalysts remains a major challenge. It is of great significance to explore non-noble metal-based electrocatalysts with efficient and stable performance for hydrogen evolution reaction (HER) in the relatively wide pH range. Herein, a self-supporting three-dimensional (3D) CoMoP-rGO/CNT catalyst was synthesized to achieve high efficiency of HER in acidic and basic solution. The combination of CNTs and rGO improves the conductivity of the substrate material, while the self-supporting structure avoids the use of the binder to expose the active sites, and the open structure of the vertically arranged CoMoP nanosheet arrays is benefit for the interaction between the electrolyte and the active sites. Thus, the CoMoP-rGO/CNT showed excellent activity and durability for HER with a low overpotential of 66 mV and 86 mV at a current density of −10 mA·cm−2 in acidic (0.5 M H 2 SO 4) and basic (1 M KOH) solution, respectively. The three-dimensional structure of CoMoP-rGO/CNT can enhance electron migration and mass transfer, while Co and Mo also play an important role in regulating surface active sites. This work may open a new way for the design of earth-rich and low-cost nanomaterials for electrocatalysis. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel concept of hierarchical-dimensional material strategy for efficient lithium storage. • High-rate Li-ion battery application and the relationship between structural hierarchy and performances. • Facile methodology for the construction of hierarchical-dimensional materials. The pulverization and aggregation of metal-based anode materials caused by considerable volume expansion during repeated lithiation/de-lithiation lead to poor lithium storage performance for lithium-ion batteries (LIBs). Herein, intricate-cavity hollow cobalt phosphide (S-CoP), which is fabricated by the weave of one-dimension (1D) hollow nanorods and further self-assemble of the weaved two-dimension (2D) substructures, is exploited as anode material to accommodate high-performance lithium storage. The self-assembled hierarchical-dimensional architecture, together with the intricate void structure of the nanorods, construct highly accessible surfaces which facilitate electrolyte wetting, diffusion distance decreasing, and thus rapid kinetics during lithium storage. Meanwhile, the developed pore volumes gifts flexible space to alleviate the huge volume change, delivering longer service life for LIBs. As a result, the LIBs based on the designed CoP afford a favorable rate behavior and stable reversible cycling performance. This work provides fresh insights in the design and construction of advanced anode materials for LIBs, which is hopeful to be also enlightening for other high-performance energy systems. [ABSTRACT FROM AUTHOR]

[Display omitted] • P-MnO 2-x was successfully prepared by a simple phosphorization process. • P-MnO 2-x exhibited excellent sensitivity and selectivity toward Pb(II). • Enhanced stripping signal based on Mn(III)/Mn(IV) cycle, oxygen vacancy sites, and surface (PO 4)3− ions was clarified. • The sensor exhibited high anti-interference and robust stability. Designed and fabricated electrochemical sensing materials with high electrical conductivity, sufficient number of active sites, and good selectivity to target analytes are highly desirable for sensitive determination of heavy metal ions in water. In this work, MnO 2 nanoflowers with enriched oxygen vacancies and surface phosphate ions (P-MnO 2-x) were prepared by a simple phosphorization process. For this novel electrode modifier, oxygen vacancies increased the electrical conductivity, thereby improving the signal-to-noise ratio of sensors. Phosphate ions acted as ligand molecules for trapping Pb(II) and thus enhanced the selectivity toward Pb(II), and through (PO 4)3− bridge, a fast charge-transfer channel was formed and promoting the redox cycles between Mn(III)/Mn(IV) and Pb(II)/Pb(0). Thus, these multiple synergistic effects endowed P-MnO 2-x with a high detection sensitivity of 50.11 μA μM−1 and a low limit of detection of 0.0012 μM. More impressively, after phosphorization treatment, P-MnO 2-x showed ultra-high selectivity toward Pb(II) while did not change the stripping signals obviously toward other common metal ions. This synergistic oxygen-vacancy and surface modulation strategy demonstrates a new way to construct high-performance electrode materials for electroanalysis. [ABSTRACT FROM AUTHOR]

3D porous Ni is fabricated via an easily scalable electroless plating method using a dynamic template formed through in-situ hydrogen bubbles. The pore size in the range of several micrometers is controllable through adjusting the Ni 2+ depositing rate and hydrogen bubbles releasing rate. The Ni 3 S 2 nanosheet arrays anode is then grown on the unique 3D porous Ni current collector followed by subsequent surface phosphorization. The tremendous interconnected pores and rich voids between the Ni 3 S 2 nanosheet arrays cannot only provide rapid transferring channels for Na + , but also accommodate volumetric changes of the Ni 3 S 2 electrode during cycling, guaranteeing the integrity of the active material. In addition, the surface phosphorized layer enhances the electronic conductivity through providing an electron transport highway along the 3D Ni 3 S 2 , NiP 2 layer, and 3D porous Ni current collector, and simultaneously stabilizes the electrode/electrolyte interphase as a protecting layer. Because of these merits, the phosphorized 3D porous Ni 3 S 2 (3D P-Ni 3 S 2 ) electrode is capable of delivering an ultra-stable capacity of 387.5 mAh g -1 at 0.1 A g -1 , and a high capacity retention of 85.3% even at a high current density of 1.6 A g -1 ., (© 2021 Wiley-VCH GmbH.)

Hollow cobalt oxide is phosphated under an inert atmosphere to form a composite with interconnected porous structures. As an electrocatalyst for oxygen evolution reaction, the catalytic activity of this material is significantly better than Co 3 O 4. [Display omitted] • Amorphous porous CoP x -CoO y complex was constructed by low temperature phosphating. • The same structure was obtained when the method is applied to other oxides. • The structure can significantly increase the number of active sites required for OER. • The catalytic activity of the material for oxygen release reaction was better than that of Co 3 O 4. Interconnected porous structures and amorphous materials are widely used in the field of electrocatalysis owing to their rich catalytic active sites. Amorphous CoP x -CoO y composites with interconnected porous structures were constructed through low-temperature phosphating of cobalt oxides. Moreover, low-temperature phosphating of cobalt oxide and other metal oxides with different morphologies also produced the same porous structures, further proving the generality of this method. Interestingly, the prepared CoP x -CoO y catalyst has excellent electrocatalytic activity for oxygen evolution reactions in alkaline media. At a current density of 10 mA cm−2, an overpotential of 322 mV and a Tafel slope of 102 mV dec-1 are generated. In a 1 M KOH electrolyte, its electrochemical activity is significantly better than that of unphosphorylated Co 3 O 4. Under catalytic conditions, the excellent performance arises from the formation of the incorporation of phosphorus, amorphous phase and porous structures. The unique structure can provide a large number of active sites, significantly shortening the electron transfer pathway. This is the foundation of our research on the development of electrocatalysts with rich active sites. The synthesis of amorphous interconnected porous structures by introducing phosphorus will allow the application of high-efficiency catalysts in electrocatalysis and other important chemical reactions. [ABSTRACT FROM AUTHOR]

[Display omitted] • The electrocatalytic activity of Ni and Co films for HER is enhanced by electro-phosphorization. • The electro-phosphorization are realized in hypophosphite solution under electric current action. • Ni film has an overpotential of 57 mV at 10 mA·cm−2 after phosphorization. The electrodeposited nickel and cobalt films are directly phosphorized in alkaline hypophosphite solution under the action of electric current. After the electro-phosphorization process, the morphology of nickel and cobalt films change obviously, and phosphorus element can be detected in the phosphorized films according to the EDS and XPS tests. The electrocatalytic performance of nickel and cobalt films for hydrogen evolution reaction are obviously enhanced by the electro-phosphorization treatment. Especially, the phosphorized nickel film has an overpotential of 57 mV at the current density of 10 mA·cm−2. [ABSTRACT FROM AUTHOR]

• O-doped NiCoP nanoneedles were synthesized by hydrothermal process and subsequent phosphorization treatment. • O-doped NiCoP electrode showed high specific area capacity and mass capacity. • The assembled hybrid supercapacitor delivered a high energy density of 30.52 Wh kg−1 at a power density of 749.36 W kg−1. • The device retained 80.47% of its capacitance over 5000 cycles. The preparation of electrode materials with high performance is of great significance to the practical application of supercapacitors. Here, O-doped NiCoP (O NiCoP) electrode material with porous nanoneedle structure was synthesized in-situ on carbon cloth by hydrothermal process and subsequent phosphorization treatment with high mass loading of 5.07 mg cm−2. The electrode combined the large specific surface area of porous nanoneedle, the high electronic conductivity of phosphide and the electronic structure regulation of oxygen element, which finally showed excellent electrochemical performance. The optimized O NiCoP electrode delivered a high specific area capacity of 3457 mC cm−2 at a current density of 1 mA cm−2 and a high specific mass capacity of 621 C g −1 at a current density of 1 A g −1. The hybrid supercapacitor composed of O NiCoP positive electrode and commercial activated carbon negative electrode exhibited a high energy density of 30.52 Wh kg−1 at a power density of 749.36 W kg−1. The hybrid supercapacitor composed of O NiCoP positive electrode and commercial activated carbon electrode exhibited high energy density and power density. Image, graphical abstract [ABSTRACT FROM AUTHOR]

The main energy consumption of industrial water electrolysis is electric energy, which accounts for ca. 80% of the total cost of water electrolysis. Developing highly efficient bifunctional electrocatalyst for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is essential to reduce the energy consumption. Herein, nickel foam (NF)-supported NiCoP nanorod array catalyst is prepared and used for HER and OER. Not only at a small current density (10 mA/cm2), but also at the commercially required high current density (≥500 mA/cm2), NiCoP/NF catalyst shows excellent bifunctional properties with extremely low overpotential and high stability. Small overpotentials of 60 and 253 mV are needed to drive the current density of 10 mA/cm2 for HER and OER, respectively, and the cell voltage of overall water splitting is only 1.55 V. At the high current density of 500 mA/cm2, the overpotentials are 180 and 365 mV, and the corresponding cell voltage is only 1.83 V. Furthermore, the cell voltage hardly changes within 24 h of overall water splitting test, which makes the catalyst have promising applications in the industrial water electrolysis. The high performance of NiCoP/NF outperforms the commercial RuO 2 -Pt/C couple and most of the bifunctional Ni/Co-based catalysts reported so far. Image 1 • Ni foam-supported NiCoP nanorod array catalyst is prepared and used for HER and OER. • Not only at low but also at high current densities, NiCoP/NF shows high activity. • NiCoP/NF requires only 1.83 V to drive 500 mA/cm2 for overall water splitting. • Hydroxides in-situ formed in the catalytic process contribute to the high activity. [ABSTRACT FROM AUTHOR]

Oxygen evolution reaction (OER) is a vital process in numerous energy conversion systems, and therefore, considerable attention has been devoted to the fabrication of nonnoble and highly efficient electrode materials for OER. Herein, Co nanoparticles embedded in the N, P-codoped porous carbon (Co/P-N-C) are synthesized using a novel Co-based metal-organic polymer (Co-MOP) as the precursor through carbonization and a subsequent phosphorization treatment process. When the phosphorization treatment is carried out at pH 3, Co/P-N-C exhibits a very low overpotential of 300 mV for a current density of 10 mA cm−2 with a small Tafel slope of 61 mV dec−1 and excellent stability over 20000 s. The electrocatalytic performance of Co/P-N-C was even better than that of the commercial RuO 2 material. Density functional theory calculations were used to simulate the electrocatalytic process and to verify the experimental findings, which showed that the superior OER performance was attributed to the active sites of doped P and Co nanoparticles. This viable strategy of using a novel Co-MOP to create a novel phosphorized Co/P-N-C microporous carbon-based material may expand the opportunities for the exploration of high-performance and robust nonnoble metal electrocatalysts for energy-conversion reactions. Co atoms on N, P co-doped porous carbon via phosphorization on Co-MOP exhibit excellent OER performance due to the synergistic effects of P and Co. Image 1 • A phosphorization strategy to prepare a porous MOP-derived Co-P-N-C nanosphere. • The as-obtained yolk-shell Co-P-N-C nanosphere possesses the high electrocatalytic activity for OER. • Reveal the P and Co synergistic mechanism for forming more active sites of Co-P-N-C. [ABSTRACT FROM AUTHOR]

A novel self-supported nickel-based honeycomb electrode with microtapered holes (NHEMH) is firstly synthesized through a fast electrodeposition method with a high current density. P-doped NHEMH with heterogeneous Ni 2 P/NiO decorated with multiple vacancies exhibits the outstanding overall water splitting performance in alkaline medium as an alkali-electrolyzer. • We firstly synthesize a novel nickel-based honeycomb electrode with microtapered holes (NHEMH) through fast electrodeposition method. • The 3D network electrode assembly with abundant microtapered holes vastly improves the electrolyte/active material contact areas. • PNHEMH delivers a lower overvoltage of 1.52 V at 10 mA/cm2 with 12 h durability. • PNHEMH with heterostructure decorated with multiple vacancies can optimize the adsorption free energy of intermediate by DFT analysis. Hydrogen production is the key to the development and utilization of hydrogen energy. In this paper, we find a new phenomenon in which abundant and uniform bubbles evolve and quickly release during water splitting on the surface of a nickel-based honeycomb electrode with microtapered holes (NHEMH). Benefiting from the unique microtapered hole honeycomb structure, the solution circulation on the surface of NHEMH is accelerated, thus generating a dynamically stabilized reactive interface and improving the ionic/mass exchange. Meanwhile, the unique honeycomb skeleton has good hydrophilicity and aerophobic properties. Furthermore, NHEMH with a large surface area, rich multi-vacancies, and highly conductive nickel metal exhibits an outstanding electrocatalytic ability. P-doped NHEMH (PNHEMH) with the Ni 2 P/NiO heterointerface decorated by multivacancies, when used as an electrolyzer for overall water splitting, requires only 1.52 V to produce a current density of 10 mA/cm2, which is much better than the performance of benchmark Pt/C//IrO 2 electrodes. [ABSTRACT FROM AUTHOR]

Electrode materials with excellent capacitance performance remain on urgent need for energy storage devices. In this study, we successfully fabricated porous P-doped carbon-supported NiCoP nanoparticles (NiCoP@P–C) by chelating sodium alginate with Ni2+ and Co2+ ions and subsequently performing a high-temperature calcination process. The carbonization process involved phosphating the metal ions to form bimetallic NiCoP nanoparticles and doping the P element into the carbon framework. The as-prepared material integrated the merits of metal phosphide (high theoretical specific capacitance), bimetal (excellent electrochemical conductivity), and porous structure (rapid ion transportation). The sample consequently exhibited outstanding electrochemical properties with an ultrahigh specific capacitance of 920 F g−1 (0.5 A g−1) and a high cycle stability of 84% over 5000 cycles with a small mass loading of 3.6 mg cm−2. Moreover, an asymmetric supercapacitor assembled with NiCoP@P–C-500 as the positive electrode and activated carbon as the negative electrode delivered a maximum energy density of 57.8 W h kg−1 at a power density of 522 W kg−1. • Ni–Co-SA beads were obtained by crosslinking sodium alginate with Ni2+ and Co2+. • The NiCoP alloys were formed during the high-temperature phosphorization process. • The NiCoP hybrid exhibited the outstanding electrochemical performance. • The NiCoP@P–C-500 hybrid showed a high specific capacitance of 920 F g−1 at 0.5 A g−1. • The NiCoP@P–C-500//AC device reached a high energy density of 57.5 W h kg−1. [ABSTRACT FROM AUTHOR]

• Develop new CoP nanocrystals by phosphating the Co 3 O 4 nanocubes precursor. • New type of non-metallic HER catalyst with initial potential of only 87 mV. • Self-assembled CoP nanocrystals with good catalytic performance. • Provide new way for preparing efficient and inexpensive HER electrocatalysts. Electrocatalytic water splitting reactions include hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). It provides an effective method for producing high-purity hydrogen as a sustainable energy source. In order to solve the growing energy shortage and environmental damage, the development and synthesis of efficient and inexpensive hydrogen evolution reaction (HER) electrocatalysts is urgently needed. Traditional reaction catalysts such as Pt/Rh/Ir and their oxides (such as IrO 2 , RuO 2) have limited their wide application as electrocatalysts due to their high prices and small reserves. In this work, CoP nanocrystals by phosphating the Co 3 O 4 nanocubes precursor were successfully synthesized. CoP nanocrystals are a new type of non-metallic HER catalyst that can work under alkaline conditions. Its initial potential is only 87 mV at a current density of 10 mA cm−2, and the Tafel slope is 105 mV dec−1. The catalyst can maintain the catalytic performance for 12 h in 1 M KOH solution, and the performance can still be maintained above 95.44%. [ABSTRACT FROM AUTHOR]

• PNCS@C assemblies are prepared through facile one-step solvothermal route and a subsequent phosphorization process. • The as-obtained product as electrode material shows a specific capacity of 1026 C g−1 at current density of 1 A g−1. • An asymmetric supercapacitor delivers an energy density of 131.40 Wh kg−1 at 1355.37 W kg−1. • The superior electrochemical performance could be attributed to their unique spatial architectures and synergistic effect. Nickel cobalt sulfides are deemed as promising electrode materials for energy storage devices due to their rich redox active sites as well as superior conductivity. Herein, we report P-doped Ni-Co-S@C (PNCS@C) assemblies consisting of many nanosheets through facile one-step solvothermal route and a subsequent phosphorization process. The as-obtained product is utilized as electrode material for supercapacitor, which shows a specific capacity of 1026 C g−1 at current density of 1 A g−1. An asymmetric supercapacitor (ASC) delivers an energy density of 131.40 Wh kg−1 at a power density of 1355.37 W kg−1. As anode material for lithium ion battery, it presents a discharge capacity of 2300.10 mAh g−1 at 0.1 A g−1. The superior electrochemical performance could be attributed to their unique spatial architectures and synergistic effect between composites. [ABSTRACT FROM AUTHOR]

• Develop new self-assembled Ni/Co phosphides composite spheres. • Carbon nanospheres via a hydrothermal process and effective manner. • Exhibit excellent HER electrocatalytic activity. • Significant potentials in composite electrocatalyst design. Because of their high catalytic activity and abundant resources, nonprecious transition metal phosphides are favorable substitutes for noble metals as hydrogen evolution reaction (HER) electrocatalysts. In this work, self-assembled Ni/Co phosphide composite N-doped carbon spheres were successfully prepared via a hydrothermal process, which had abundant exposed active sites for the HER. The as-obtained samples exhibited excellent electrocatalytic activity for the HER with an overpotential of only 160 mV (vs. RHE) at a current density of 10 mA cm−2 in a 0.5 M H 2 SO 4 solution and a comparatively low Tafel slope (57 mV dec−1). Additionally, the Ni 2 P/CoP spheres also show good stability after 120 h and 5000 cycles of a cyclic voltammetry test. Their highly efficient catalytic activity for the HER is attributed to the specific spherical structure, which provides exposed Ni 2 P and CoP for favorable adsorption and desorption of hydrogen. Therefore, nonprecious transition metal phosphide spheres may provide a promising strategy to improve the catalytic activity of HER electrocatalysts. [ABSTRACT FROM AUTHOR]

Design and develop of cost-effective non-enzymatic electrode materials is of great importance for next generation of glucose sensors. In this work, we report a high-performance self-supporting electrode fabricated via direct epitaxial growth of nickel phosphide on Ni foam (Ni 2 P/NF) for nonenzymatic glucose sensors in alkaline solution. Under the optimal conditions, the uniform Ni 2 P nanosheets could be obtained with an average thickness of 80 nm, which provides sufficient active sites for glucose molecules. As a consequence, the Ni 2 P/NF electrode displays superior electrochemistry performances with a high sensitivity of 6375.1 μ A mM -1 cm -2 , a quick response about 1 s, a low detection limit of 0.14 μ M (S/N = 3), and good selectivity and specificity. Benefit from the strong interaction between Ni 2 P and NF, the Ni 2 P/NF electrode is also highly stable for long-term applications. Furthermore, the Ni 2 P/NF electrode is capable of analyzing glucose in human blood serum with satisfactory results, indicating that the Ni 2 P/NF is a potential candidate for glucose sensing in real life., (© 2021 IOP Publishing Ltd.)

Constructing well-defined nanointerfaces is vital to enhance the catalytic performances through electronic coupling effects from different components. However, it is still a challenge to construct metal selenides-based interfacial nanomaterials with satisfactory oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performances for overall water splitting. Herein, sandwich-like structured NiSe 2 /Ni 2 P@FeP nanosheet arrays are rationally constructed, which starts from NiSe 2 arrays directly on carbon cloth as backbones, followed by coating FeP nanoparticles on the backbones through the phosphorization process. Further, abundant nanointerfaces with rich defects and disordered structure are constructed during the phosphorization process, which can boost the charge transfer rate and provide rich electroactive sites. Consequently, as-synthesized NiSe 2 /Ni 2 P@FeP nanosheet arrays exhibit good HER and OER performances with small overpotentials, low Tafel slopes and good stability. Further, the overall water splitting device built by NiSe 2 /Ni 2 P@FeP exhibits a voltage of 1.554 V to attain 10 mA cm−2. Our current work may provide some new insights on rationally constructing nanointerfaces with rich defects to boost the catalytic performances for overall water splitting. Image 1 • A two-step strategy is developed to construct NiSe 2 /Ni 2 P@FeP electrocatalysts. • The abundant interfaces can boost transfer rate and provide rich active sites. • NiSe 2 /Ni 2 P@FeP exhibits superior activities and stability in HER and OER tests. • A low voltage of 1.554 V is achieved at 10 mA cm−2 for the constructed full-cell. [ABSTRACT FROM AUTHOR]

Highlights from the article: Hydrogen Evolution: Embedding RhPx in N, P Co-Doped Carbon Nanoshells Through Synergetic Phosphorization and Pyrolysis for Efficient Hydrogen Evolution (Adv. Funct. Keywords: carbon nanoshells; hydrogen evolution reaction; phosphorization; pyrolysis; RhPx Pyrolysis, hydrogen evolution reaction, phosphorization, carbon nanoshells, RhPx.

Owning to the energy crisis and environmental pollution, it is urgent to develop an efficient and earth‐abundant electrocatalyst for water splitting. In this work, the Cu2O cubes are first synthesized through a modified precipitation method, and it is subsequently selected as the Cu2+ source to synthesize 3D MOF (metal‐organic framework, Cu‐BDC) nanoarray by a facile and efficient bottom‐up method. Next, porous Cu3P@C is prepared via the low‐temperature phosphorization of 3D Cu‐BDC nanoarray as a high‐performance electrocatalyst for oxygen and hydrogen evolution reactions (OER and HER). In particular, the effect of reaction temperature on the morphology of 3D Cu‐BDC precursor is studied in detail. Experimental results reveal that Cu3P@C‐120 derived from sea urchin‐like Cu‐BDC exhibits excellent electrocatalytic performance owning to the high special surface area, developed porous structure, and the uniform dispersion of Cu3P nanoparticles, which affords the current density of 10 mA cm−2 at low overpotentials of 300 and 124 mV for OER (alkaline medium) and HER (acidic medium) with Tafel slopes of 24 and 29 mV dec−1, respectively. Remarkably, Cu3P@C‐120 also exhibits an excellent durability for OER and HER, making it an efficient bifunctional electrocatalyst for application in the production of clean hydrogen fuel. [ABSTRACT FROM AUTHOR]

Application of transition metal phosphides (TMPs) for electrochemical energy conversion and storage has great potential to alleviate the energy crisis. Although there are many methods to get TMPs, it is still immensely challenging to fabricate hierarchical porous TMPs with superior electrochemical performances by a simple, green, and secure approach. Herein, we report a facile method to synthesize the CoP/C nanoboxes by pyrolysis of phytic acid (PA) cross-linked Co complexes that are acquired from reaction of PA and ZIF-67. The PA can not only slowly etch ZIF-67 and gain a hollow structure but also act as a source of phosphorus to prepare CoP/C nanoboxes. The CoP/C nanoboxes deliver an ultrahigh specific capacity (868 mA h g -1 at 100 mA g -1 ) and excellent cycle stability (523 mA h g -1 after 1000 cycles at 500 mA h g -1 ) when used as anode materials for lithium-ion batteries. Moreover, when used as an electrocatalyst for hydrogen evolution reaction, the CoP/C nanoboxes exhibit ultralow overpotential, small Tafel slope, and excellent durability in acidic media. The method to produce CoP/C nanoboxes is easy and environmentally friendly and can be readily extended to design other TMPs/C nanocomposites.