Ni-P共觸媒裝載的鍺摻雜α-Fe2O3光陽極應用於HMF選擇性氧化為FDCA;Selective Photoelectrochemicl oxidation of 5- Hydroxymethylfurfural to 2,5-Furandicarboxylic acid on Nickel Phosphate decorated Germanium doped hematite photoanode

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Title:	Ni-P共觸媒裝載的鍺摻雜α-Fe2O3光陽極應用於HMF選擇性氧化為FDCA;Selective Photoelectrochemicl oxidation of 5- Hydroxymethylfurfural to 2,5-Furandicarboxylic acid on Nickel Phosphate decorated Germanium doped hematite photoanode
Authors:	李文豪;Li, Wen-Hao
Contributors:	化學工程與材料工程學系
Keywords:	光電化學;氧化鐵;選擇性氧化;光觸媒薄膜;5-羥甲基糠醛;2,5-?喃二甲酸;Photoelectrochemical(PEC);Selective oxidation;α-Fe2O3;5-Hydroxymethylfurfural(HMF);2,5-Furandicarboxylic acid(FDCA)
Date:	2021-09-06
Issue Date:	2021-12-07 11:31:01 (UTC+8)
Publisher:	國立中央大學
Abstract:	利用氧化生物質 (Biomass) 取代光電化學 (Photoelectrochemical, PEC) 系統中光陽極較不符合動力學的產氧反應，生成高經濟價值的生質化學品，代替石化燃料。本實驗選用地表蘊藏豐富、能帶位置合適且能隙狹窄的 Hematite (α-Fe2O3) 作為光觸媒，去選擇性氧化木質纖維衍生物 5- Hydroxymethylfurfural (HMF)，生成可聚合成聚2,5-?喃二甲酸乙二酯 (PEF) 樹脂的 2,5-Furandicarboxylic acid (FDCA)。α-Fe2O3 擁有更穩定的光電化學特性可供長時間使用，適合作為選擇性氧化的光陽極材料。利用水熱法 (Hydrothermal) 製備 α-Fe2O3 光陽極薄膜，並適量摻雜前驅液穩定的鍺 (Ge) 元素來增加 α- Fe2O3 電子的濃度，優化電子的傳輸，提高材料的導電性，減少電子－電洞再結合，提升光電流值約4倍。選定碳酸-碳酸氫鈉緩衝液作為電解液，其能夠維持α-Fe2O3 的光電化學表現且不與 HMF 反應，提供選擇性氧化良好的環境。為提高 FDCA 的選擇性，在 α-Fe2O3 表面裝載 Ni-P、Co-P 等共觸媒，並在電解液中加入氧化媒介－TEMPO，幫助 HMF 轉化成 FDCA。電沉積 Ni-P 共觸媒30分鐘能讓光電流更穩定，減少衰弱，幫助光電化學的表現。30 min Ni-P / Ge-doped α-Fe2O3 於加入1 mM HMF 與5 mM TEMPO 的碳酸-碳酸氫鈉緩衝電解液擁有最好的結果，經過24小時實驗，裝載 Ni-P 將FDCA 的選擇率從原本的51 %提升至59 %，生成率也從40 %增加到49 %，而第二產物 FFCA 選擇率從32 %降至29 %，HMF 的轉化率更高達83 %，由此可知，α-Fe2O3 適合做為 HMF 選擇性氧化的光電極，而Ni-P 共觸媒能有效幫助 FDCA 的生成，為適性的氧化共觸媒。 ;Anode oxygen evolution reaction ( OER ) is not kinetically favorable in photoelectrochemical ( PEC ) cell. Therefore, it is feasible to replace OER by producing the value-added biomass chemicals. In this work, we used hematite ( α-Fe2O3 ) modified with germanium ( Ge ) and Nickel Phosphate ( NiP ) cocatalyst as photoanode to oxidize 5- Hydroxymethylfurfural ( HMF ) to 2,5-Furandicarboxylic acid ( FDCA ). First, Ge-doped α-Fe2O3 thin film was synthesized using hydrothermal method with the addition of germanium oxide into iron oxide precursor. Proper amount of Ge doping can increase the charge densities carriers and improve the charge transfer in photoanode. The photocurrent exhibited four times higher than that of the pristine sample ( at 1.23 VRHE in 1 M NaOH ). After that, through the PEC measurement and reaction test in different basic and buffer solutions, we found that carbonate-bicarbonate solution at pH = 10.6 gave a high current and did not react with HMF. 2,2,6,6-Tetramethylpiperidine 1-oxyl ( TEMPO ) as a mediator can facilitate the selective oxidation of HMF. Besides, nickel phosphate ( NiP ) cocatalyst on Ge-doped α-Fe2O3 also improve the selectivity of FDCA. The photocurrent density of modified anode was higher and more stable in the electrolyte composed of HMF and TEMPO. With electrodeposition time of NiP increasing to 30 min, FDCA achieved 48 % yield and a selectivity up to 59 % after 24 hours, which was 16 % higher than that of Ge-doped α-Fe2O3 without cocatalyst. The conversion of HMF was 83 % and secondary derivative FFCA had only 29 % selectivity.
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