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氢能是最具发展前景的清洁可再生能源之一, 绿色制氢技术备受关注. 电解水制氢因反应过程环保、产物纯度高且操作简便, 被视为实现规模化绿氢生产的重要途径. 然而, 电解水催化剂普遍存在成本高昂、合成工艺复杂等问题, 严重制约了该技术在新能源领域的产业化应用. 低温等离子体技术凭借其低温高效、高反应活性及独特的电磁场效应, 在功能材料表面改性领域展现出显著优势. 本文系统综述了低温等离子体技术在电解水催化材料制备与改性中的应用, 重点探讨等离子体改性的作用机制, 对电催化反应效率的提升效果. 首先阐述了典型非平衡低温等离子体的物理特性与作用原理; 继而分类评述了近年来该技术在催化材料改性中的研究进展, 包括表面微结构调控、表面物性调控及界面优化等策略; 最后, 基于当前改性机理与应用研究的局限性, 对低温等离子体技术在催化剂设计中的未来发展方向提出了展望.Hydrogen energy, as one of the most promising clean and renewable energy sources, has received much attention due to its green production technology. Electrolytic water splitting is regarded as a critical pathway for large-scale green hydrogen production due to its environmentally friendly reaction process, high product purity, and operational simplicity, However, electrocatalysts for water electrolysis commonly face challenges such as high costs and complex synthesis processes, thereby severely hindering the industrial application. Low-temperature plasma (LTP) technology, with its advantages of mild processing conditions, high reactivity, and unique electromagnetic field effects, has demonstrated remarkable potential in the surface modification of materials. This review systematically summarizes the applications of LTP in the preparation and modification of electrocatalytic materials for water splitting, focusing on the mechanism of plasma-induced enhancement in electrocatalytic efficiency. First, the physical characteristics and fundamental principle of typical non-equilibrium low-temperature plasma are elucidated. Subsequently, recent advances in plasma-assisted modification strategies for catalytic materials are categorized and critically discussed, including surface microstructure modulation, surface property regulation and interface optimization. Finally, based on the current limitations in mechanistic understanding and practical applications, future research directions for LTP technology in catalyst design are proposed.
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Keywords:
- plasma /
- material preparation /
- material modification /
- electrocatalysis
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图 2 (a) 双朗缪尔探针的I-V曲线[32]; (b) 朗缪尔探针与非侵入式阻抗等离子体密度测量结果对比图[33]; (c) P-Ar-H2等离子体和Ar-CH4等离子体的光学发光光谱[34]; (d) 氧气气氛的光学发光光谱[35]; (e) 不同压力下介质阻挡放电等离子体放电图像[36]; (f) 不同压力下氮气的发射强度[36]
Fig. 2. (a) I-V curve of double Langmuir probe[32]; (b) comparison of Langmuir probe non-invasive impedance plasma density[33]; (c) in suit optical emission spectra of plasma of P-Ar-H2 and Ar-CH4[34]; (d) optical emission spectroscopy of O2 atmosphere[35]; (e) discharge images of DBD at different pressures[36]; (f) emission intensities of N2 at different pressures[36].
图 3 (a), (b) L-Co纳米结构形成示意图和扫描电子显微镜图像[37]; (c) Co2P-Ni2P/CC扫描电子显微镜图像[38]; (d) 富氧NiFe-LDH的透射电子显微镜图像[39]; (e) 富氧NiFe-LDH纳米片的比表面积和孔径分布[39]; (f) P-Ni MOF/POM制备流程图[40]; (g) Ni MOF/POM扫描电子显微镜图像[40]; (h) 多孔P-Ni MOF/POM扫描电子显微镜图像[40]; (i) Ni3N/NF的扫描电子显微图像[41]; (j) N2-H2等离子体下Ni3N/NF合成示意图[41]
Fig. 3. (a), (b) Schematic illustration for the formation and SEM images of L-Co NSs[37]; (c) SEM images of Co2P-Ni2P/CC[38]; (d) TEM images of oxygen-enriched NiFe-LDH[39]; (e) BET and pore diameter distribution of oxygen-enriched NiFe-LDH nanosheets[39]; (f) schematic illustration of the fabrication process of porous P-Ni MOF/ POM[40]; (g) SEM image of Ni MOF/POM[40]; (h) SEM images of P-Ni MOF/ POM[40]; (i) SEM image of Ni3N/NF[41]; (j) schematic illustration of the synthesis of Ni3N/NF under N2-H2 plasma[41].
图 4 (a)—(c) NiFeP/NF合成示意图、NiFe/NF和NiFeP/NF的扫描电子显微镜图像[44]; (d) CoPO合成示意图[45]; (e), (f) ZIF-67和CoPO的扫描电子显微镜图像[45]; (g), (h) 磷化前后的T-NiMoP电子显微镜图像[46]; (i) Co2N的扫描电子显微镜图像[47]
Fig. 4. (a)–(c) Synthesis process of NiFeP/NF and SEM images of NiFeMOF/NF and NiFeP/NF[44]; (d) synthesis process of CoPO[45]; (e), (f) SEM image of ZIF-67 and CoPO[45]; (g), (h) SEM image of P-NiMoP and T-NiMoP[46]; (i) SEM image of Co2N[47].
图 5 (a), (b) NiCo-LDHs和NiCo-LDHs/Ar的扫描电子显微镜图像[50]; (c), (d) 等离子体处理前后的氢氧化镍纳米片的扫描电子显微镜图像[51]; (e) 等离子体处理前后MoS2的透射电子显微镜图像[48]; (f), (g) 等离子体剥离前后的MXene材料的扫描电子显微镜图像[52]; (h), (i) MXene和MXene-DBD的扫描电子显微镜图像[53]
Fig. 5. (a), (b) SEM images of NiCo-LDHs and NiCo-LDHs/Ar[50]; (c), (d) SEM images of m-Ni(OH)2NASs and β-Ni(OH)2/Ni NSAs[51]; (e) TEM images of MoS2 after plasma treatment[48]; (f), (g) SEM images of MXene@GO and MXene@rGO[52]; (h), (i) SEM images of MXene and MXene-DBD[53].
图 6 (a)—(c) 纳米颗粒晶格间距的高分辨透射电子显微镜、O 1s轨道的X射线光电子能谱、纳米颗粒的带隙测定[58]; (d)—(f) N2等离子体处理不同时间的电子顺磁共振光谱、O 1s轨道的X射线光电子能谱、N2等离子体处理后的NiMoO4的高分辨率透射电镜图像[59]; (g) 不同条件等离子体处理的傅里叶转换光谱; (h) PBA-raw和PBA-3h-A的电子自旋共振光谱; (i) 等离子体处理后的PBA的水接触角[60]
Fig. 6. (a)–(c) HRTEM image showing lattice spacing of the nanoparticle, XPS spectra of the O 1s, bandgap determination of the nanoparticles[58]; (d)–(f) EPR spectra by N2 plasma for different periods, XPS spectra of the O 1s and HRTEM image of NiMoO4 under N2 plasma treated[59]; (g) Fourier transform infrared spectra of plasma treated under different conditions; (h) solid electron spin resonance spectra of PBA-raw and PBA-3h-A; (i) water contact angle (WCA) of plasma treated PBA[60].
图 7 (a), (b) Ar/NH3等离子体处理前后的拉曼光谱和热重曲线[63]; (c), (d) 氧化钴异质结经氧等离子体处理前后的拉曼光谱和N2吸附-脱附等温曲线[64]; (e), (f) 氮掺杂纳米管经Ar等离子体处理前后的拉曼光谱和C 1s轨道的X射线光电子能谱[65]
Fig. 7. (a), (b) Raman spectra and Thermogravimetry (TGA) curves before and after Plasma treatment[63]; (c), (d) Raman spectra and N2 adsorption-desorptionisotherms of cobalt oxide heterojunctions before and after oxygen plasma treatment[64]; (e), (f) Raman spectra and XPS spectra of the C 1s of nitrogen-doped nanotubes before and after Ar plasma treatment[65].
图 8 (a) NiFeP/NF, NiFe MOF/NF和NiFe LDH/NF的X射线衍射[44]; (b) NiFeP/NF的高分辨率透射电镜图像[44]; (c) CoNiP@C/NF的X射线衍射[68]; (d) CoNiP@C和CoNiP的P 2p轨道的X射线光电子能谱[68]; (e)—(g) N2-H2和纯N2的光发射光谱、不同等离子体处理后氢氧化镍的X射线衍射、N2-H2等离子体处理后Ni 2p的XPS光谱[69]; (h), (i) N2-H2等离子体处理NiV LDH的X射线衍射和Ni 1s轨道的X射线光电子能谱[70]
Fig. 8. (a) X-ray diffraction (XRD) of NiFeP/NF, NiFeMOF/NF, and NiFeLDH/NF[44]; (b) HR-TEM images of NiFeP/NF[44]; (c) XRD patterns of CoNiP@C/NF[49]; (d) XPS spectra of P 2p of CoNiP@C and CoNiP[68]; (e)–(g) optical emission spectra of N2-H2 and N2, XRD of Ni(OH)2 after different plasma treatment and XPS spectra of Ni 2p after N2-H2 plasma treatments[69]; (h), (i) XRD pattern and Ni 1s XPS spectra of the NiV LDH after N2-H2 plasma treatment[70].
图 9 (a) Co2P和Ni2P的高分辨率透射电子显微图像[71]; (b) 基于Co2P-Ni2P/CC中生物电化学体统(BEF)的电子转移示意图[71]; (c) 等离子体进行磷氮掺杂的NiCo泡沫高分辨率透射电子显微镜图像[72]; (d) CoO/Co的高分辨率透射电子显微镜图像[73]; (e) v-CoO/Co(111), Co(111)和v-CoO的态密度和d带中心[74]; (f) IrO2/CoCH异质结构透射电子显微镜图像[75]; (g) CoCH, IrO2和IrO2/CoCH的电子态密度[75]; (h) Ni12P5/ZnP2异质结构的透射电子显微镜图像[75]; (i) N2吸附-脱附等温线(孔径分布曲线)[75]
Fig. 9. (a) High-resolution transmission electron microscopy images of Co2P and Ni2P[71]; (b) schematic diagram of electron transfer based on BEF in Co2P-Ni2P/CC[71]; (c) high-resolution transmission electron microscopy images of plasma phosphorus-nitrogen doped NiCo foam[72]; (d) the HRTEM of CoO/Co [73]; (e) DOS and d-band centers of -CoO/Co(111), Co(111), v-CoO[73]; (f) the HRTEM images of heterostructure of IrO2/CoCH[74]; (g) the DOS of CoCH, IrO2 and IrO2/CoCH[75]; (h) the TEM images of the heterostructure of Ni12P5/ZnP2[75]; (i) N2 adsorption–desorption isotherms(BJH) [75].
表 1 不同低温非平衡等离子体的典型参数
Table 1. Typical plasma parameters in different low temperature non-equilibrium plasma.
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