Kwon Youngkook, Birdja Yuvraj Y, Raoufmoghaddam Saeed, Koper Marc T M
Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden (The Netherlands), Fax: (+31) 071-527-4451.
ChemSusChem. 2015 May 22;8(10):1745-51. doi: 10.1002/cssc.201500176. Epub 2015 Apr 23.
Electrocatalytic hydrogenation of 5-hydroxymethylfurfural (HMF) is studied on solid metal electrodes in acidic solution (0.5 M H2 SO4 ) by correlating voltammetry with on-line HPLC product analysis. Three soluble products from HMF hydrogenation are distinguished: 2,5-dihydroxymethylfuran (DHMF), 2,5-dihydroxymethyltetrahydrofuran (DHMTHF), and 2,5-dimethyl-2,3-dihydrofuran (DMDHF). Based on the dominant reaction products, the metal catalysts are divided into three groups: (1) metals mainly forming DHMF (Fe, Ni, Cu, and Pb), (2) metals forming DHMF and DMDHF depending on the applied potentials (Co, Ag, Au, Cd, Sb, and Bi), and (3) metals forming mainly DMDHF (Pd, Pt, Al, Zn, In, and Sb). Nickel and antimony are the most active catalysts for DHMF (0.95 mM cm(-2) at ca. -0.35 VRHE and -20 mA cm(-2) ) and DMDHF (0.7 mM cm(-2) at -0.6 VRHE and -5 mA cm(-2) ), respectively. The pH of the solution plays an important role in the hydrogenation of HMF: acidic condition lowers the activation energy for HMF hydro-genation and hydrogenates the furan ring further to tetrahydrofuran.
通过将伏安法与在线高效液相色谱产物分析相关联，研究了酸性溶液（0.5 M H₂SO₄）中固体金属电极上5-羟甲基糠醛（HMF）的电催化氢化反应。区分了HMF氢化反应的三种可溶产物：2,5-二羟甲基呋喃（DHMF）、2,5-二羟甲基四氢呋喃（DHMTHF）和2,5-二甲基-2,3-二氢呋喃（DMDHF）。根据主要反应产物，将金属催化剂分为三组：（1）主要生成DHMF的金属（Fe、Ni、Cu和Pb），（2）根据施加电位生成DHMF和DMDHF的金属（Co、Ag、Au、Cd、Sb和Bi），以及（3）主要生成DMDHF的金属（Pd、Pt、Al、Zn、In和Sb）。镍和锑分别是生成DHMF（在约-0.35 VRHE和-20 mA cm⁻²时为0.95 mM cm⁻²）和DMDHF（在-0.6 VRHE和-5 mA cm⁻²时为0.7 mM cm⁻²）的最活性催化剂。溶液的pH值在HMF的氢化反应中起重要作用：酸性条件降低了HMF氢化反应的活化能，并使呋喃环进一步氢化成四氢呋喃。
