非贵金属催化剂在羟甲基糠醛电氧化增值中的应用 高等学校化学学报    2023, 44 (5): 20220710-.   DOI:10.7503/cjcu20220710

Fig.4 Morphological features of Ni₂P NPA/NF and conversation of FDCA^[50]
（A） XRD pattern of Ni₂P NPA/NF with the corresponding standard patterns of Ni₂P and Ni； （B， C） SEM images of Ni₂P NPA/NF with different magnifications； （D） SEM and the corresponding elemental mapping images of Ni₂P NPA/NF； （E） LSV curves of Ni₂P NPA/NF at a scan rate of 2 mV/s in 1.0 mol/L KOH with and without 10 mmol/L HMF； （F） conversion and yield（%） changes of HMF and its oxidation products during the electrochemical oxidation of HMF at 1.423 V（vs. RHE） in 1.0 mol/L KOH with 10 mmol/L HMF； （G） faradaic efficiencies of Ni₂P NPA/NF for FDCA production under three successive electrolysis cycles.
Copyright 2016， Wiley-VCH GmbH.

正文中引用本图/表的段落

本文讨论的过渡金属Xide催化剂包括过渡金属硫化物、 磷化物、 氮化物及硼化物等. 已有大量的工作集中在过渡金属Xide催化剂的设计制备上， 如通过硫化反应， 可以在泡沫镍表面形成一层均匀的Ni₃S₂， 从而形成Ni₃S₂/NF电极［49］. 将该电极作为工作电极， 在10 mmol/L HMF+1 mol/L KOH电解液中进行恒电位极化测试（1.423 V vs. RHE）. 当通过约58 C的电量后， 生成FDCA的转化率和法拉第效率都接近100%（由HPLC及1H NMR测试结果计算所得）， 说明过渡金属硫化物催化剂对于HMFOR的催化活性和选择性较高. 同时， 在HMFOR过程中几乎没有检测到DFF， 说明在Ni₃S₂/NF催化剂表面， HMFOR主要沿着HMF→HMFCA→FFCA→FDCA的路径进行. 类似地， Ni₂P/NF催化剂在1.423 V（vs. RHE）恒电位极化测试下也展现了接近100%的选择性和较好的稳定性（图4）； 其HMFOR也主要沿着HMF→HMFCA→FFCA→FDCA的路径进行［50］. 除了硫化物和磷化物， 过渡金属硼化物也展现了较好的HMFOR性能. 如采用CoB催化剂， 在1.45 V电极电势下可以实现98%的法拉第效率， 而FDCA的产率也高达94%； 如采用泡沫镍作为集流体担载CoB催化剂， 1.45 V下法拉第效率和FDCA产率都接近100%［53］. Brawe等［52］在泡沫镍上制备了Ni _x B催化剂， 该催化剂具有100%的法拉第效率和98.5%的 FDCA选择性. 另一方面， Zhou等［61］报道过渡金属氮化物有望成为有前景的HMFOR催化剂. 如将Ni₃N颗粒包覆在碳层中可以有效地提升其稳定性， 经过6次HMFOR测试后， FDCA产率仍高于98%［51］.

本文的其它图/表

• Fig.1  Schematic illustration of HMF and its possible oxidation products
• Table 1  The value-added products derived from HMFOR and their possible applications
• Fig.2  TEM image of Pd₁Au₂/C catalyst(A) and product distribution on Pd₁Au₂/C for the oxidation of 0.02 mol/L HMF in 0.1 mol/L KOH(B)^[28]Copyright 2014， the Royal Society of Chemistry.
• Fig.3  Schematic of the electrochemical cells with Co⁃P/CF catalyzed HMF oxidation(A), concentrations of HMF and oxidation products over passed charge during the chronoamperometry experiment conducted at 1.423 V in 1.0 mol/L KOH containing 50 mmol/L HMF(B)^[47], conversion and yield(%) changes of HMF and its oxidation products during the electrochemical oxidation of HMF at 1.54 V in a 0.5 mol/L borate buffer solution containing 5 mmol/L HMF and 7.5 mmol/L TEMPO(C)^[48]（A， B） Copyright 2016， American Chemical Society； （C） Copyright 2015， Nature Publishing Group.
• Table 2  Typical non-precious metal catalysts and their HMFOR performances
• Table 3  The oretical ΔH_f^FERE and experimental ΔH_f^exp of several typical transition metal-based compounds^[60]
• Fig.5  Sum Frequency Generation(SFG) spectra recorded at the working electrode/electrolyte interface after running the cell at various voltages for 90 min(A) and by monitoring the reaction at different times at 1.45 V(vs. RHE) in 1 mol/L KOH and 20 mmol/L HMF(B)^[51]Copyright 2019， Wiley-VCH GmbH.
• Table 4  Typical transition metal Xides and their derivates(real active materials) during anodic reactions
• Fig.6  Physical characterizations of the reconstructed Ni(OH)₂/NiFeP after potentiostatic HMFOR polarization
• Fig.7  Theoretical calculation results to unravel the underlying HMFOR mechanisms on CuO⁃PdO catalyst^[83]（A） Adsorption configuration of the HMF and OH on CuO（111） surface and the as-designed CuO-PdO； （B） HMF and OH adsorption free energy； （C） free energy diagram and adsorption configurations of HMFOR intermediates on CuO（111） and CuO⁃PdO； （D） promoting mechanism of the HMFOR； （E） the charge density difference of PdO on CuO（111） surface.Copyright 2022， Wiley-VCH GmbH.
• Fig.8  Electrochemical HMFOR performance using NiFe⁃LDHs catalyst^[57]（A） HPLC chromatogram traces of the various products at different reaction times following an HMF electrochemical oxidation reaction； （B） digital photograph showing the color change of the anodic electrolyte during the electrochemical HMF oxidation process； （C） concentration changes of HMF and its oxidation products with the time of chronoamperometric tests at 1.33 V vs. RHE； （D） HMF concentration changes during four successive cycles.Copyright 2018， American Chemical Society.