鎳鉬鋅合金微柱、微螺旋之製備及其在1M KOH中之產氫行為探討;Preparation of Ni-Mo-Zn Alloy micropillars and Microspirals and Investigation of Their Hydrogen Production Behavior in 1M KOH

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题名:	鎳鉬鋅合金微柱、微螺旋之製備及其在1M KOH中之產氫行為探討;Preparation of Ni-Mo-Zn Alloy micropillars and Microspirals and Investigation of Their Hydrogen Production Behavior in 1M KOH
作者:	黃楚雯;Huang, Chu-Wen
贡献者:	機械工程學系
关键词:	微陽極引導電鍍;鎳鉬鋅合金;微螺旋;產氫;非貴金屬催化劑;Micro-anode guided electroplating;NiMoZn alloy;Micro-helix;Hydrogen production;Non-precious metal catalyst
日期:	2022-08-26
上传时间:	2022-10-04 12:14:54 (UTC+8)
出版者:	國立中央大學
摘要:	鎳基金屬是工業電解水製造氫氣之熱門陰極材料。近幾年來，新開發的鎳鋅、鎳鉬等二元合金，在陰極產氫應用表現優異。本研究中藉由合金中所含之金屬鋅，在鹼性溶液中溶蝕後，可增加合金電極產氫催化電極之表面積，增加產氫活性。與鎳搭配鉬元素具有協同效應，改變d軌道的電子密度，從而降低金屬表面上的ΔGH(free energy for hydrogen adsorption)，提高氫還原的催化活性。以上兩點進行發想，然而以微陽極導引製程(Micro-anode guided electroplating, MAGE)製備鎳鉬鋅三元合金。電鍍製程中透過改變鍍浴中鉬酸鈉含量(0.02 M~0.26 M)與析鍍間距(35 µm~65 µm)對合金微柱的表面形貌、化學組成、晶體結構、機械性質進行討論。並且將不同之鎳鉬鋅合金微柱，浸入至1 M KOH中，使用循環伏安法、塔弗極化曲線、計時電位法量測、電化學阻抗分析，探討其產氫性能表現。結果顯示: 在鍍浴中鉬酸鈉濃度為0.10 M，並且電壓為4.2 V與析鍍間距為35 µm的條件下，所微電鍍出的10/35微柱(Ni29.4Mo66.9Zn3.7)，具有最好的產氫效率。有最小的Tafel斜率(79 mV/dec)與最大的交換電流密度值(3.1 mA/cm2)。在循環伏安曲線中具有最低產氫起始電位(-0.17 V vs. RHE)與最大的陰極峰值電流密度(651 mA/cm2)。在-300 mA/cm2下的計時電位法，具有最小的電位(-0.42 V vs. RHE)。在-200 mA/cm2下的產氫電化學阻抗分析，具有最小的電荷轉移阻抗(4.54 Ω•cm2)。以微陽極引導電鍍法製備之鎳鉬鋅合金微柱為鹼性水溶液電解產氫之潛力材料。 ;Nickel-based metals are popular cathode materials for industrial water electrolysis to produce hydrogen. In recent years, newly developed binary alloys such as nickel-zinc and nickel-molybdenum have performed well in the application of cathode hydrogen production. In this study, the metal zinc contained in the alloy can be dissolved in an alkaline solution to increase the surface area of the hydrogen-producing catalytic electrode of the alloy electrode to increase the hydrogen-producing activity. And through the synergistic effect of nickel and molybdenum, the electron density of the d orbital is changed, thereby changing the ΔGH on the metal surface and improving the catalytic activity of hydrogen reduction. The nickel-molybdenum-zinc ternary alloy was prepared by Micro-anode guided electroplating (MAGE). During the electroplating process, the surface morphology, chemical composition, crystal structure, and mechanical properties of the alloy micropillars were discussed by changing the sodium molybdate content (0.02 M~0.26 M) and the distance between anode and cathode (35 μm~65 μm) in the plating bath. And different nickel-molybdenum-zinc alloy micropillars were soaked in 1 M KOH solution. The hydrogen production performance was discussed by cyclic voltammetry, hydrogen production polarization curve, chronopotentiometry measurement, and electrochemical impedance analysis. The results show that when the concentration of sodium molybdate in the plating bath is 0.10 M, and the voltage is 4.2 V and the distance between cathode and anode is 35 μm, the electroplated 10/35 micropillars (Ni29.4Mo66.9Zn3.7) have the highest good hydrogen production efficiency.It has the smallest Tafel slope (79 mV/dec) and the largest exchange current density value (3.1 mA/cm2). It has the lowest hydrogen production onset potential (-0.17 V vs. RHE) and the highest cathodic peak current density (651 mA/cm2) in the cyclic voltammetry curve. Chronopotentiometry at -300 mA/cm2 with the smallest potential (-0.42 V vs. RHE). Chronopotentiometry at -300 mA/cm2. Electrochemical impedance analysis of hydrogen production at -200 m, with the smallest charge transfer impedance (4.54 Ω•cm2). The nickel-molybdenum-zinc alloy micropillars prepared by the micro-anode-guided electroplating method are potential materials for hydrogen production by electrolysis of alkaline aqueous solution.
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