羥胺(NH2OH)是化學工業的重要含氮原料。傳統的羥胺合成方法利用氨作為氮源，需要苛刻的反應條件，導致不利的環境影響。取而代之在這裡我們使用電催化合成羥胺，但由於 NH2OH 作為中間體的不穩定性，高價值羥胺的選擇性合成具有挑戰性。在這項工作中，我們展示了本質上具有較好羥胺脫附能力的Bi，在酸性條件下選擇性和快速地將硝酸鹽還原為羥胺。基材選用酸性下耐腐蝕之Ti、Cu、C結合電鍍Bi，結果顯示在-0.4vsRHECu/Bi羥胺達FE77.8%; 在-0.6vsRHE C/Bi 羥胺達FE81.2%後續針對Ti/Bi雙金屬效應去做改善分別探討電鍍Bi、無電鍍Bi、電解液含有200ppmBi離子於不同電位下電催化效應結果顯示在-0.6vsRHE羥胺FE: 200ppmBi 76.83%、無電鍍鈦鉍達70.1%。由於無電鍍鈦鉍有良好的電催化活性，後續對無電鍍Ti/Bi探討材料成長機制，發現不同結構的變化。總的來說，我們的工作提供了一種在更溫和的條件下從更簡單的原料高效合成羥胺的可行方法，為化學工業的可持續轉型做出了貢獻。

Hydroxylamine (NH₂OH) is a valuable nitrogen-containing intermediate widely used in chemical manufacturing. Conventional synthesis routes typically rely on ammonia as the nitrogen source and require harsh reaction conditions, resulting in significant environmental burdens. In this study, we present an electrocatalytic approach for the selective synthesis of hydroxylamine under mild acidic conditions. Bismuth (Bi), known for its favorable NH₂OH desorption properties, was employed as the active catalyst. Electroplated Bi on corrosion-resistant substrates (Ti, Cu, and C) demonstrated high Faradaic efficiencies (FE), achieving 77.8% on Cu/Bi at −0.4 V vs RHE and 81.2% on C/Bi at −0.6 V vs RHE.
Further optimization explored the bimetallic Ti/Bi system, comparing electroplated Bi, non-electroplated Bi, and electrolytes containing 200 ppm Bi ions. At −0.6 V vs RHE, hydroxylamine FE reached 76.83% with Bi ions and 70.1% with non-electroplated Ti/Bi. The latter exhibited promising electrocatalytic activity, prompting investigation into its growth mechanism and structural evolution.
Overall, this work offers a sustainable and efficient strategy for hydroxylamine production from simpler precursors, contributing to greener practices in the chemical industry.

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