- 导读
本研究针对过渡金属硒化物在析氢反应（HER）和超级电容器应用中存在的活性位点不足、反应动力学迟缓及导电性不佳等关键挑战，提出了一种多策略协同优化方法。通过整合缺陷工程（硒空位）、异质界面构建（MnSe/NiSe₂）及杂原子掺杂策略，所制备的 MnSe1-x-NiSe1-x/NPC（NPC代表氮、磷共掺杂碳）展现出优异的碱性析氢活性（10/100 mA cm⁻¹ 电流密度下过电位分别为 72.5 和 111.6 mV）与高能量密度超级电容器性能（在 0.799 kW kg⁻¹ 功率密度下能量密度达 71.8 Wh kg⁻¹）。结合同步辐射 X 射线吸收近边结构（XANES）、原位光谱及密度泛函理论（DFT）计算获得的机理认知，阐明了界面电子转移路径、析氢反应过程中动态水分解行为、储能过程中可逆相变机制，以及通过 d 轨道杂化优化氢氧根离子（OH⁻）/ 氢吸附质（H*）吸附能的内在规律。该研究为同步构建硒空位与异质界面提供了新颖的设计策略，也为电催化与储能系统的发展提供了重要参考。
- 成果掠影
近日，莆田学院的易明杰教授/黄建辉教授和哈尔滨工业大学的张嘉恒教授，针对过渡金属硒化物在析氢反应（HER）和超级电容器应用中存在的活性位点不足、反应动力学迟缓及导电性不佳等关键挑战，提出了一种多策略协同优化方法。通过整合缺陷工程（硒空位）、异质界面构建（MnSe/NiSe₂）及杂原子掺杂策略，所制备的 MnSe1-x-NiSe1-x/NPC（NPC 代表氮、磷共掺杂碳）展现出优异的碱性析氢活性（10/100 mA cm⁻¹ 电流密度下过电位分别为 72.5 和 111.6 mV）与高能量密度超级电容器性能（在 0.799 kW kg⁻¹ 功率密度下能量密度达 71.8 Wh kg⁻¹）。结合同步辐射 X 射线吸收近边结构（XANES）、原位光谱及密度泛函理论（DFT）计算获得的机理认知，阐明了界面电子转移路径、析氢反应过程中动态水分解行为、储能过程中可逆相变机制，以及通过 d 轨道杂化优化氢氧根离子（OH⁻）/ 氢吸附质（H*）吸附能的内在规律。该研究为同步构建硒空位与异质界面提供了新颖的设计策略，也为电催化与储能系统的发展提供了重要参考。
该成果以莆田学院为第一单位以题目“Synergistic Engineering of Heterointerfaces and Defects in N, P-Codoped Carbon-Encapsulated MnSe/NiSe2 Heterostructure for Efficient Alkaline Hydrogen Evolution and High-Performance Flexible Supercapacitors”发表在中科院一区top期刊Energy Storage Materials，影响因子为20.2。
三、核心创新点
该研究核心创新点在于提出多策略协同优化方案，同步解决过渡金属硒化物在电催化与储能应用中的关键瓶颈。通过整合缺陷工程（构建硒空位）、异质界面构建（形成 MnSe/NiSe₂异质结构）及 N、P 杂原子掺杂，结合碳封装设计，协同提升材料活性位点数量、电荷传输效率与反应动力学。借助同步辐射 XANES、原位光谱及 DFT 计算，从原子层面揭示界面电子转移、水分解机制及吸附能优化规律，阐明多策略协同作用本质。所制备的 MnSe1-X-NiSe2-X/NPC 材料同时实现优异碱性析氢活性与高能量密度储能性能，为同步构建缺陷与异质界面的多功能材料设计提供了新颖范式。
四、数据概览
Fig. 1. (a) Illustration of the preparation process of MnSe1-x-NiSe2-x/NPC. (b, c) SEM images and (d) TEM image of NiMn-ILs-MOF. (e, f) SEM images and (g) TEM image of MnNi/NPC. (h) SEM image and (i) TEM image of MnSe1-x-NiSe2-x/NPC. (j) High-resolution TEM image (Inset: GPA analysis of MnSe1-x-NiSe2-x/NPC), (k, l) inverse FFT lattice image and (m, n) lattice spacing of MnSe1-x-NiSe2-x/NPC. (o) Heterostructure model of MnSe1-x-NiSe2-x, (p) Mapping of MnSe1-x-NiSe2-x/NPC. (q-s) Water contact angles of MnSe1-x-NiSe2-x/NPC, NiSe2-x/NPC and MnSe1-x/NPC.
Fig. 2. (a) XRD of MnSe1-x-NiSe2-x/NPC. (b) BET of MnSe1-x-NiSe2-x/NPC. (c) Electron Paramagnetic Resonance spectrum of MnSe1-x-NiSe2-x/NPC, NiSe2-x/NPC, and MnSe1-x/NPC. (d) Electron density difference images of MnSe1-x-NiSe2-x/NPC, XPS of (e) Mn 2p, (f) Ni 2p, (g) Se 3d in MnSe1-x-NiSe2-x/NPC, NiSe2-x/NPC, MnSe1-x/NPC and (h) C 1s in MnSe1-x-NiSe2-x/NPC. Total density of states (TDOS) for (i) MnSe1-x-NiSe2-x, (j) MnSe1-x, and (k) NiSe2-x. XANES spectra of MnSe1-x-NiSe2-x/NPC and its comparative materials at (l) Ni K-edge and (m) Mn K-edge. The corresponding FT-EXAFS curves of MnSe1-x-NiSe2-x/NPC and its comparative materials at (n) Ni K-edge and (o) Mn K-edge. WT-EXAFS plots of MnSe1-x-NiSe2-x/NPC and its comparative materials at (p) Ni K-edge and (q) Mn K-edge.
Fig. 3. (a) The illustration of the reaction process of HER. (b) HER polarization curve. (c) Tafel plots and (d) the calculated electrochemical parameters of MnSe1-x-NiSe2-x/NPC, Pt/C, NiSe2-x/NPC and MnSe1-x/NPC in 1.0 M KOH. (e) Comparison of the HER overpotential of MnSe1-x-NiSe2-x/NPC with reference electrocatalysts. (f) The estimated amounts of gas produced over MnSe1-x-NiSe2-x/NPC. (g) CV graphs of the MnSe1-x-NiSe2-x/NPC electrode at different scan rates. (h) Cdl and relative electrochemically active surface area of MnSe1-x-NiSe2-x/NPC and other references in 1.0 M KOH. (i) Normalized with ECSA in 1.0 M KOH. (j) Cycling stability of MnSe1-x-NiSe2-x/NPC at 10 mA cm–2 for 100 h in 1.0 M KOH. (k) HER polarization curve for 1st and 1000th in 1.0 M KOH. (l) XRD results after HER in 1.0 M KOH. (m) SEM images of MnSe1-x-NiSe2-x/NPC.
Fig. 4. (a) Schematic of in situ Raman. (b) Operando 2D Raman contour plot. (c) Deconvolution of O-H stretching modes. (d) In situ spectra of interfacial water. (e) Potential-dependent normalized vO-H intensity at MnSe1-x-NiSe2-x/NPC. (f) Stark tuning rate of vO-H vibration. (g) Proposed HER mechanism in alkaline electrolyte and (h) corresponding free energy profile.
Fig. 5. (a) Schematic of the supercapacitor reaction process. (b) CV curves of MnSe1-x-NiSe2-x/NPC at different scan rates. (c) Comparative CV curves of MnSe1-x-NiSe2-x/NPC and its reference materials. (d) GCD curves of MnSe1-x-NiSe2-x/NPC at different current densities. (e) Comparative GCD curves abd (f) Rate capability of the MnSe1-x-NiSe2-x/NPC and its reference materials. (g) Specific capacity comparison with reported samples. (h) EIS and (i) Cycling performance of MnSe1-x-NiSe2-x/NPC and its reference materials. (j) Determination of b-values. (k) CV curves measured at 100 mV s-1 of MnSe1-x-NiSe2-x/NPC. (l) Capacitive versus diffusion-controlled contributions for for MnSe1-x-NiSe2-x/NPC. (m) Optimized *OH adsorption configurations. (n) HER free energy diagram of MnSe1-x-NiSe2-x/NPC and its reference materials.
Fig. 6. (a) The illustration of the as-assembled MnSe1-x-NiSe2-x/NPC/AC flexibilible device. (b) CV curves of MnSe1-x-NiSe2-x and AC at 20 mV s–1. CV curves of MnSe1-x-NiSe2-x/NPC in at (c) various potential and (d) various different scan rates. (e) GCD curves and (f) specific capacitance at different current densities. (g) Ragone plots of the present device as compared with previously reported ones. (h) GCD and (i) CV curves of MnSe1-x-NiSe2-x/NPC at under 4 A g–1 and 20 mV s–1 of bending. (j) Schematic of the in situ XRD. (k) XRD patterns and (l) operando Raman patterns of the 2D color-filled contour plot of MnSe1-x-NiSe2-x/NPC. (m) Cycling performance and (n) Coulombic efficiency of MnSe1-x-NiSe2-x/NPC at 4 A g–1 current density. (o) A fan powered by the flexible asymmetric supercapacitor device.
五、成果启示
该研究的成果启示主要体现在三方面。其一，多策略协同设计是突破单一改性局限的关键，缺陷工程、异质界面构建与杂原子掺杂的组合，为同步优化材料活性、导电性及稳定性提供了可复制思路。其二，跨表征技术联用（同步辐射 XANES + 原位光谱 + DFT 计算）为解析多组分协同作用机制提供了高效范式，助力从原子层面指导材料精准设计。其三，多功能一体化材料设计可实现电催化与储能性能的兼顾，为开发适配柔性电子、氢能制备等场景的复合型器件奠定基础，也为过渡金属化合物在能源领域的高性能应用开辟了新路径。
