Induced Anionic Functional Group Orientation-Assisted Stable Electrode-Electrolyte Interphases for Highly Reversible Zinc Anodes.

Dendrite growth and other side-reaction problems of zinc anodes in aqueous zinc-ion batteries heavily affect their cycling lifespan and Coulombic efficiency, which can be effectively alleviated by the application of polymer-based functional protection layer on the anode. However, the utilization rate of functional groups is difficult to improve without destroying the polymer chain. Here, a simple and well-established strategy is proposed by controlling the orientation of functional groups (─SO3H) to assist the optimization of zinc anodes. Depending on the electrostatic effect, the surface-enriched ─SO3H groups increase the ionic conductivity and homogenize the Zn2+ flux while inhibiting anionic permeation. This approach avoids the destruction of the polymer backbone by over-sulfonation and amplifies the effect of functional groups. Therefore, the modified sulfonated polyether ether ketone (H-SPEEK) coating-optimized zinc anode is capable of longtime stable zinc plating/stripping, and moreover an enhanced cycling steadiness under high current densities is also detected in a series of Zn batteries with different cathode materials, which achieved by the inclusion of H-SPEEK coating without causing any harmful effects on the electrolyte and cathode. This work provides an easy and efficient approach to further optimize the plating/stripping of cations on metal electrodes, and sheds lights on the scale-up of high-performance aqueous zinc-ion battery technology.

Thermal-Rectified Gradient Porous Polymeric Film for Solar-Thermal Regulatory Cooling.

Solar-thermal regulation concerning thermal insulation and solar modulation is pivotal for cooling textiles and smart buildings. Nevertheless, a contradiction arises in balancing the demand to prevent external heat infiltration with the efficient dissipation of excess heat from enclosed spaces. Here, a concentration-gradient polymerization strategy is presented for fabricating a gradient porous polymeric film comprising interconnected polymeric microspheres. This method involves establishing an electric field-driven gradient distribution of charged crosslinkers in the precursor solution, followed by subsequent polymerization and freeze-drying processes. The resulting porous film exhibits a significant porosity gradient along its thickness, leading to exceptional unidirectional thermal insulation capabilities with a thermal rectification factor of 21%. The gradient porous film, with its thermal rectification properties, effectively reconciles the conflicting demands of diverse thermal conductivity for cooling unheated and spontaneously heated enclosed spaces. Consequently, the gradient porous film demonstrates remarkable enhancements in solar-thermal management, achieving temperature reductions of 3.0 and 4.1 °C for unheated and spontaneously heated enclosed spaces, respectively, compared to uniform porous films. The developed gradient-structured porous film thus holds promise for the development of thermal-rectified materials tailored to regulate solar-thermal conditions within enclosed environments.

Langmuir-Blodgett Film Formed by Amphiphilic Molecules for Facile and Rapid Construction of Zinc-Iodine Cell.

Zinc-iodine batteries (ZIBs) are promising candidates for ecofriendly, safe, and low-cost energy storage systems, but polyiodide shuttling and the complex cathode fabrication procedures have severely hindered their broader commercial usage. Herein, a protocol is developed using phospholipid-like oleylamine molecules for scalable production of Langmuir-Blodgett films, which allows the facile preparation of ZIB cathodes in less than 1 min. The resulting inhomogeneous cathode allows for the continuous conversion of iodine. Moreover, the amine group of the oleylamine molecule at the cathode is capable of producing [OA*I+]I3- charge-transfer complexes with iodine, which facilitates the rapid migration of iodine and results in a highly reversible iodine conversion process. Consequently, the as-prepared ZIBs can deliver over 2000 cycles at 0.5 mA cm-2 with a capacity retention of 75.3%. This work presents a novel, straightforward, and efficient method for the rapid construction of ZIBs.

Highly Porous Yet Transparent Mechanically Flexible Aerogels Realizing Solar-Thermal Regulatory Cooling.

The demand for highly porous yet transparent aerogels with mechanical flexibility and solar-thermal dual-regulation for energy-saving windows is significant but challenging. Herein, a delaminated aerogel film (DAF) is fabricated through filtration-induced delaminated gelation and ambient drying. The delaminated gelation process involves the assembly of fluorinated cellulose nanofiber (FCNF) at the solid-liquid interface between the filter and the filtrate during filtration, resulting in the formation of lamellar FCNF hydrogels with strong intra-plane and weak interlayer hydrogen bonding. By exchanging the solvents from water to hexane, the hydrogen bonding in the FCNF hydrogel is further enhanced, enabling the formation of the DAF with intra-layer mesopores upon ambient drying. The resulting aerogel film is lightweight and ultra-flexible, which possesses desirable properties of high visible-light transmittance (91.0%), low thermal conductivity (33 mW m-1 K-1), and high atmospheric-window emissivity (90.1%). Furthermore, the DAF exhibits reduced surface energy and exceptional hydrophobicity due to the presence of fluorine-containing groups, enhancing its durability and UV resistance. Consequently, the DAF has demonstrated its potential as solar-thermal regulatory cooling window materials capable of simultaneously providing indoor lighting, thermal insulation, and daytime radiative cooling under direct sunlight. Significantly, the enclosed space protected by the DAF exhibits a temperature reduction of 2.6 °C compared to that shielded by conventional architectural glass.

Cation Substitution Strategy for Developing Perovskite Oxide with Rich Oxygen Vacancy-Mediated Charge Redistribution Enables Highly Efficient Nitrate Electroreduction to Ammonia.

The electrocatalytic nitrate (NO3-) reduction reaction (eNITRR) is a promising method for ammonia synthesis. However, its efficacy is currently limited due to poor selectivity, largely caused by the inherent complexity of the multiple-electron processes involved. To address these issues, oxygen-vacancy-rich LaFe0.9M0.1O3-δ (M = Co, Ni, and Cu) perovskite submicrofibers have been designed from the starting material LaFeO3-δ (LF) by a B-site substitution strategy and used as the eNITRR electrocatalyst. Consequently, the LaFe0.9Cu0.1O3-δ (LF0.9Cu0.1) submicrofibers with a stronger Fe-O hybridization, more oxygen vacancies, and more positive surface potential exhibit a higher ammonia yield rate of 349 ± 15 µg h-1 mg-1cat. and a Faradaic efficiency of 48 ± 2% than LF submicrofibers. The COMSOL Multiphysics simulations demonstrate that the more positive surface of LF0.9Cu0.1 submicrofibers can induce NO3- enrichment and suppress the competing hydrogen evolution reaction. By combining a variety of in situ characterizations and density functional theory calculations, the eNITRR mechanism is revealed, where the first proton-electron coupling step (*NO3 + H+ + e- → *HNO3) is the rate-determining step with a reduced energy barrier of 1.83 eV. This work highlights the positive effect of cation substitution in promoting eNITRR properties of perovskites and provides new insights into the studies of perovskite-type electrocatalytic ammonia synthesis catalysts.

Bio-Inspired Aerobic-Hydrophobic Janus Interface on Partially Carbonized Iron Heterostructure Promotes Bifunctional Nitrogen Fixation.

Competition from hydrogen/oxygen evolution reactions and low solubility of N2 in aqueous systems limited the selectivity and activity on nitrogen fixation reaction. Herein, we design an aerobic-hydrophobic Janus structure by introducing fluorinated modification on porous carbon nanofibers embedded with partially carbonized iron heterojunctions (Fe3 C/Fe@PCNF-F). The simulations prove that the Janus structure can keep the internal Fe3 C/Fe@PCNF-F away from water infiltration and endow a N2 molecular-concentrating effect, suppressing the competing reactions and overcoming the mass-transfer limitations to build a robust "quasi-solid-gas" state micro-domain around the catalyst surface. In this proof-of-concept system, the Fe3 C/Fe@PCNF-F exhibits excellent electrocatalytic performance for nitrogen fixation (NH3 yield rate up to 29.2 µg h-1 mg-1 cat. and Faraday efficiency (FE) up to 27.8 % in nitrogen reduction reaction; NO3 - yield rate up to 15.7 µg h-1 mg-1 cat. and FE up to 3.4 % in nitrogen oxidation reaction).

Visible-Light Transparent, Ultrastretchable, and Self-Healable Semicrystalline Fluorinated Ionogels for Underwater Strain Sensing.

The development of ultrastretchable ionogels with a combination of high transparency and unique waterproofness is central to the development of emerging skin-inspired sensors. In this study, an ultrastretchable semicrystalline fluorinated ionogel (SFIG) with visible-light transparency and underwater stability is prepared through one-pot copolymerization of acrylic acid and fluorinated acrylate monomers in a mixed solution of poly(ethylene oxide) (PEO) and fluorinated ionic liquids. Benefiting from the formation of the PEO-chain semicrystalline microstructures and the abundant noncovalent interactions (reversible hydrogen bonds and ion-dipole interactions) in an ionogel, SFIG is rendered with room-temperature stable cross-linking structures, providing high mechanical elasticity as well as high chain segment dynamics for self-healing and efficient energy absorption during the deformation. The resultant SFIG exhibits excellent stretchability (>2500%), improved mechanical toughness (7.4 MJ m-3), and room-temperature self-healability. Due to the high compatibility and abundance of hydrophobic fluorinated moieties in the ionogel, the SFIG demonstrates high visible-light transparency (>97%) and excellent waterproofness. Due to these unique advantages, the as-prepared SFIG is capable of working as an ultrastretchable ionic conductor in capacitive-type strain sensors, demonstrating excellent underwater strain-sensing performances with high sensitivity, large detecting range, and exceptional durability. This work might provide a straightforward and efficient method for obtaining waterproof ionogel elastomers for application in next-generation underwater sensors and communications.

Soluble porous organic cages as homogenizers and electron-acceptors for homogenization of heterogeneous alloy nanoparticle catalysts with enhanced catalytic activity.

The creation of ultrafine alloy nanoparticles (<5 nm) that can maintain surface activity and avoid aggregation for heterogeneous catalysis has received much attention and is extremely challenging. Here, ultrafine PtRh alloy nanoparticles imprisoned by the cavities of reduced chiral covalent imine cage (PtRh@RCC3) are prepared successfully by an organic molecular cage (OMC) confinement strategy, while the soluble RCC3 can act as a homogenizer to homogenize the heterogeneous PtRh alloy in solution. Moreover, the X-ray absorption near-edge structure (XANES) results show that the RCC3 can act as an electron-acceptor to withdraw electrons from Pt, leading to the formation of higher valence Pt atoms, which is beneficial to improving the catalytic activity for the reduction of 4-nitrophenol. Attributed to the synergistic effect of Pt/Rh atoms and the unique function of the RCC3, the reaction rate constants of Pt1Rh16@RCC3 are 49.6, 8.2, and 5.5 times than those of the Pt1Rh16 bulk, Pt@RCC3 and Rh@RCC3, respectively. This work provides a feasible strategy to homogenize heterogeneous alloy nanoparticle catalysts in solution, showing huge potential for advanced catalytic application.

Semicrystalline Conjugated Polymers with Well-Defined Active Sites for Nitrogen Fixation in a Seawater Electrolyte.

Faradaic efficiency for the nitrogen reduction reaction (NRR) is often limited by low N2 solubility in the electrolyte, while a large number of intimate contacts between the electrolyte and solid catalyst can also inevitably sacrifice many active sites for the NRR. Here, it is reported that a "quasi-gas-solid" interface formed in donor-acceptor-based conjugated polymers (CPs) is beneficial to boosting the NRR process and at the same time suppressing the competing hydrogen evolution reaction. Of particular interest, it is found that a semicrystalline CP catalyst, SC-PBDT-TT, exhibits a high Faradaic efficiency of up to 60.5% with a maximum NH3 production rate of 16.8 µg h-1 mg-1 in a neutral-buffered seawater electrolyte. Molecular dynamics and COMSOL Multiphysics simulations reveal the origin of the observed high NRR performance arising from the presence of desirable crystal regions to resist the penetration of H2 O molecules, leading to the formation of a "quasi-gas-solid" interface inside the catalyst for a favorable direct-contact between the catalyst and N2 molecules. Furthermore, high-throughput computations, based on density functional theory, reveal the actual real active site for N2 adsorption and reduction in SC-PBDT-TT. This work provides a new framework for optimizing NRR performance of metal-free catalysts by controlling their crystallinities.

A Universal Spinning-Coordinating Strategy to Construct Continuous Metal-Nitrogen-Carbon Heterointerface with Boosted Lithium Polysulfides Immobilization for 3D-Printed LiS Batteries.

Constructing intimate coupling between transition metal and carbon nanomaterials is an effective means to achieve strong immobilization of lithium polysulfides (LiPSs) in the applications of lithium-sulfur (LiS) batteries. Herein, a universal spinning-coordinating strategy of constructing continuous metal-nitrogen-carbon (MNC, M = Co, Fe, Ni) heterointerface is reported to covalently bond metal nanoparticles with nitrogen-doped porous carbon fibers (denoted as M/MN@NPCF). Guided by theoretical simulations, the Co/CoN@NPCF hybrid is synthesized as a proof of concept and used as an efficient sulfur host material. The polarized CoNC bridging bonds can induce rapid electron transfer from Co nanoparticles to the NPCF skeleton, promoting the chemical anchoring of LiPSs to improve sulfur utilization. Hence, the as-assembled LiS battery presents a remarkable capacity of 781 mAh g-1 at 2.0 C and a prominent cycling lifespan with a low decay rate of only 0.032% per cycle. Additionally, a well-designed Co/CoN@NPCF-S electrode with a high sulfur loading of 7.1 mg cm-2 is further achieved by 3D printing technique, which demonstrates an excellent areal capacity of 6.4 mAh cm-2 at 0.2 C under a lean-electrolyte condition. The acquired insights into strongly coupled continuous heterointerface in this work pave the way for rational designs of host materials in LiS systems.

Recent advances and perspectives of 3D printed micro-supercapacitors: from design to smart integrated devices.

3D-printed micro-supercapacitors (MSCs) have emerged as the ideal candidates for energy storage devices owing to their unique characteristics of miniaturization, structural diversity, and integration. Exploring the 3D printing technology for various materials and architectures of MSCs is key to realizing customization and optimizing the performance of 3D-printed MSCs. In this review, we summarize the latest progress in 3D-printed MSCs with regards to general printing approaches, printable materials, and rational design considerations. Specifically, several general types of 3D printing techniques (their working principles, available materials, resolutions, advantages, and disadvantages) and their applications to fabricate electrodes with different energy storage mechanisms, and various electrolytes, are summarized. We further discuss research directions in terms of integrated systems with other electronics. Finally, future perspectives on the research and development directions in this important field are further discussed.

Homogeneous electric field and Li+ flux regulation in three-dimensional nanofibrous composite framework for ultra-long-life lithium metal anode.

Lithium (Li) metal is considered as the best anode candidate for next-generation high-energy batteries due to its ultralow electrochemical potential and extremely high theoretical capacity. However, issues arising from the undesired growth of lithium dendrites and infinite volumetric change have seriously hindered the practical application of lithium metal batteries (LMBs). Here, we designed a super-lithiophilic amorphous zinc oxide-doped carbon nanofiber framework with uniformly-distributed and parallel multichannels (MCCNF@ZnO) to achieve the homogeneous distribution of electric field and Li+ flux. By the assistances of COMSOL Multiphysics simulations and ex-situ scanning electron microscopy, we reveal that the Li metal preferentially deposits into the porous nanochannels inside the nanofibers, followed by its even distribution on the lithiophilic surface of MCCNF@ZnO. Furthermore, the conductive multichannels of the carbon nanofiber skeleton can effectively minimize the partial current density, thereby effectively avoiding the electrochemical polarization and assisting the uniform metallic deposition. As a result, MCCNF@ZnO exhibits a stable CE over 99.2% as the substrate after 500 cycles at the current density of 1 mA cm-2. The symmetrical cell of lithium-loaded MCCNF@ZnO composite electrodes can stably operate over 3300 h at 0.5 mA cm-2, indicating the great potential of MCCNF@ZnO for stabilizing lithium metal anodes in practical applications of LMBs.

Asymmetric Sodiophilic Host Based on a Ag-Modified Carbon Fiber Framework for Dendrite-Free Sodium Metal Anodes.

Sodium (Na) metal is considered a promising anode material for high-energy Na batteries due to its high theoretical capacity and abundant resources. However, uncontrollable dendrite growth during the repeated Na plating/stripping process leads to the issues of low Coulombic efficiency and short circuits, impeding the practical applications of Na metal anodes. Herein, we propose a silver-modified carbon nanofiber (CNF@Ag) host with asymmetric sodiophilic features to effectively improve the deposition behavior of Na metal. Both density functional theory (DFT) calculations and experiment results demonstrate that Na metal can preferentially nucleate on the sodiophilic surface with Ag nanoparticles and uniformly deposit on the whole CNF@Ag host with a "bottom-up growth" mode, thus preventing unsafe dendrite growth at the anode/separator interface. The optimized CNF@Ag framework exhibits an excellent average Coulombic efficiency of 99.9% for 500 cycles during Na plating/stripping at 1 mA cm-2 for 1 mAh cm-2. Moreover, the CNF@Ag-Na symmetric cell displays stable cycling for 500 h with a low voltage hysteresis at 2 mA cm-2. The CNF@Ag-Na//Na3V2(PO4)3 full cell also presents a high reversible specific capacity of 102.7 mAh g-1 for over 200 cycles at 1 C. Therefore, asymmetric sodiophilic engineering presents a facile and efficient approach for developing high-performance Na batteries with high safety and stable cycling performance.

Gradient phosphorus-doping engineering and superficial amorphous reconstruction in NiFe2O4 nanoarrays to enhance the oxygen evolution electrocatalysis.

A better solid-liquid-gas three-phase boundary is vital for low energy cost oxygen evolution reaction (OER), making the designed regulation of interfacial atmosphere necessary. Herein, we find that the OER electrocatalysis can be dramatically improved by synergistically forming disordered electronic structures and superficial amorphous layers, as superficial oxyhydroxide, phosphorus-doped NiFe2O4 nanoarrays on nitrogen-doped carbon nanofibers (OP-NiFe2O4/NCNFs). Unveiled by the depth-profiling analysis from the X-ray photoelectron spectroscopy, the contents of phosphorous doping in the OP-NiFe2O4 nanoarrays change dynamically from outside to inside due to its in situ superficial reconstruction into the oxyhydroxide layer, thereby accelerating electron transfer between heterogeneous phases. As revealed by density functional theory calculations, this amorphous oxyhydroxide layer and dynamically varied phosphorous content would positively shift the d-band center of the NiFe2O4-related compounds, leading to lower adsorption energy towards water molecule. Thus, the OP-NiFe2O4/NCNF electrocatalyst displays a low overpotential of 260 mV at a current density of 10 mA cm-2 and a small Tafel slope of 44.8 mV dec-1 in an alkaline medium.

Tracking Airborne Molecules from Afar: Three-Dimensional Metal-Organic Framework-Surface-Enhanced Raman Scattering Platform for Stand-Off and Real-Time Atmospheric Monitoring.

Stand-off Raman spectroscopy combines the advantages of both Raman spectroscopy and remote detection to retrieve molecular vibrational fingerprints of chemicals at inaccessible sites. However, it is currently restricted to the detection of pure solids and liquids and not widely applicable for dispersed molecules in air. Herein, we realize real-time stand-off SERS spectroscopy for remote and multiplex detection of atmospheric airborne species by integrating a long-range optic system with a 3D analyte-sorbing metal-organic framework (MOF)-integrated SERS platform. Formed via the self-assembly of Ag@MOF core-shell nanoparticles, our 3D plasmonic architecture exhibits micrometer thick SERS hotspot to allow active sorption and rapid detection of aerosols, gas, and volatile organic compounds down to parts-per-billion levels, notably at a distance up to 10 m apart. The platform is highly sensitive to changes in atmospheric content, as demonstrated in the temporal monitoring of gaseous CO2 in several cycles. Importantly, we demonstrate the remote and multiplex quantification of polycyclic aromatic hydrocarbon mixtures in real time under outdoor daylight. By overcoming core challenges in current remote Raman spectroscopy, our strategy creates an opportunity in the long-distance and sensitive monitoring of air/gaseous environment at the molecular level, which is especially important in environmental conservation, disaster prevention, and homeland defense.

Ion-Selective Polyamide Acid Nanofiber Separators for High-Rate and Stable Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have attracted great attention because of their high energy density and high theoretical capacity. However, the "shuttle effect" caused by the dissolution of polysulfides in liquid electrolytes severely hinders their practical applications. Herein, we originally propose a carboxyl functional polyamide acid (PAA) nanofiber separator with dual functions for inhibiting polysulfide transfer and promoting Li+ migration via a one-step electrospinning synthesis method. Especially, the functional groups of -COOH in PAA separators provide an electronegative environment, which promotes the transport of Li+ but suppresses the migration of negative polysulfide anions. Therefore, the PAA nanofiber separator can act as an efficient electrostatic shield to restrict the polysulfide on the cathode side, while efficiently promoting Li+ transfer across the separator. As a result, an ultralow decay rate of only 0.12% per cycle is achieved for the PAA nanofiber separator after 200 cycles at 0.2 C, which is less than half that (0.26% per cycle) of the commercial Celgard separator.

Shape-dependent thermo-plasmonic effect of nanoporous gold at the nanoscale for ultrasensitive heat-mediated remote actuation.

Nanoporous gold (NPG) promises efficient light-to-heat transformation, yet suffers limited photothermal conversion efficiency owing to the difficulty in controlling its morphology for the direct modulation of thermo-plasmonic properties. Herein, we showcase a series of shape-controlled NPG nanoparticles with distinct bowl- (NPG-B), tube- (NPG-T) and plate-like (NPG-P) structures for quantitative temperature regulation up to 140 °C in <1 s using laser irradiation. Notably, NPG-B exhibits the highest photothermal efficiency of 68%, which is >12 and 39 percentage points better than those of other NPG shapes (NPG-T, 56%; NPG-P, 49%) and Au nanoparticles (29%), respectively. We attribute NPG-B's superior photothermal performance to its >13% enhanced light absorption cross-section compared to other Au nanostructures. We further realize an ultrasensitive heat-mediated light-to-mechanical "kill switch" by integrating NPG-B with a heat-responsive shape-memory polymer (SMP/NPG-B). This SMP/NPG-B hybrid is analogous to a photo-triggered mechanical arm, and can be activated swiftly in <4 s simply by remote laser irradiation. Achieving remotely-activated "kill switch" is critical in case of emergencies such as gas leaks, where physical access is usually prohibited or dangerous. Our work offers valuable insights into the structural design of NPG for optimal light-to-heat conversion, and creates opportunities to formulate next-generation smart materials for on-demand and multi-directional responsiveness.

Sulfur-Deficient Bismuth Sulfide/Nitrogen-Doped Carbon Nanofibers as Advanced Free-Standing Electrode for Asymmetric Supercapacitors.

The use of free-standing carbon-based hybrids plays a crucial role to help fulfil ever-increasing energy storage demands, but is greatly hindered by the limited number of active sites for fast charge adsorption/desorption processes. Herein, an efficient strategy is demonstrated for making defect-rich bismuth sulfides in combination with surface nitrogen-doped carbon nanofibers (dr-Bi2 S3 /S-NCNF) as flexible free-standing electrodes for asymmetric supercapacitors. The dr-Bi2 S3 /S-NCNF composite exhibits superior electrochemical performances with an enhanced specific capacitance of 466 F g-1 at a discharge current density of 1 A g-1 . The high performance of dr-Bi2 S3 /S-NCNF electrodes originates from its hierarchical structure of nitrogen-doped carbon nanofibers with well-anchored defect-rich bismuth sulfides nanostructures. As modeled by density functional theory calculation, the dr-Bi2 S3 /S-NCNF electrodes exhibit a reduced OH- adsorption energy of -3.15 eV, compared with that (-3.06 eV) of defect-free bismuth sulfides/surface nitrogen-doped carbon nanofiber (df-Bi2 S3 /S-NCNF). An asymmetric supercapacitor is further fabricated by utilizing dr-Bi2 S3 /S-NCNF hybrid as the negative electrode and S-NCNF as the positive electrode. This composite exhibits a high energy density of 22.2 Wh kg-1 at a power density of 677.3 W kg-1 . This work demonstrates a feasible strategy to construct advanced metal sulfide-based free-standing electrodes by incorporating defect-rich structures using surface engineering principles.

Engineering a nanotubular mesoporous cobalt phosphide electrocatalyst by the Kirkendall effect towards highly efficient hydrogen evolution reactions.

Tailoring the size and controlling the morphology of particular nano-architectures are considered as two promising strategies to improve the catalytic performance of metal nanocrystals towards hydrogen evolution reactions (HERs). Herein, mesoporous cobalt phosphide nanotubes (CoP-NTs) with a three-dimensional network structure have been obtained through a facile and efficient electrospinning technique combined with thermal stabilization and phosphorization treatments. The thermal stabilization process has been demonstrated to play a key role in the morphological tailoring of Co3O4 nanotubes (Co3O4-NTs). As a result, the CoP-NTs show one-dimensional hollow tubular architecture instead of forming a worm-like tubular CoP structure (W-CoP-NTs) or severely aggregated CoP powder (CoP-NPs) which originate from the Co3O4 nanotubes without thermal stabilization treatment and Co3O4 nanoparticles, respectively. Satisfyingly, under an optimized phosphorization degree, the CoP-NT electrode exhibits a low onset overpotential of 53 mV with a low Tafel slope of 50 mV dec-1 during the HER process. Furthermore, the CoP-NT electrode is capable of driving a large cathodic current density of 10 mA cm-2 at an overpotential of 152 mV, which is much lower than those of its contrast samples, i.e. CoP-NPs (211 mV) and W-CoP-NTs (230 mV). Therefore, this work provides a feasible and general strategy for constructing three-dimensionally organized mesoporous non-noble metal phosphide nanotubes as promising alternative high-performance electrocatalysts for the commercial platinum ones.