Research progress in anode transition metal-based catalysts for direct methanol fuel cell
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摘要: 發展可替代能源對緩解全球能源問題具有重要意義。直接甲醇燃料電池（DMFC）因其工作溫度低、能量密度高以及低污染物排放特性正逐漸成為最有發展前景的便攜式能源技術之一。目前，其商業化進程主要取決于陽極甲醇氧化反應（MOR）的動力學快慢。貴金屬作為最常用的陽極催化劑得到了廣泛的研究，但是其稀缺性以及易受COads中間產物中毒影響限制了其應用。考慮到以上問題，具有優異抗中毒能力的低Pt或者非Pt納米催化劑的設計和研發變得十分重要。本文從DMFC陽極電催化原理出發，總結了過渡金屬基催化劑（過渡金屬?貴金屬催化劑、過渡金屬催化劑以及自支撐催化劑）在MOR中的研究進展。重點強調了納米催化劑的組成成分、多孔結構、高指數面、晶體缺陷以及頂點增強效應等對其電化學性能的影響。最后，展望了過渡金屬基電催化劑在DMFC中所面臨的機遇和挑戰。Abstract: The development of alternative energy resources is of great significance to alleviate the global energy issue. The direct methanol fuel cell (DMFC) is gradually becoming one of the most promising portable energy technologies due to the merits of low operating temperature, high energy density, and low pollutant emission. Currently, its commercialization process mainly depends on the kinetics of the anodic methanol oxidation reaction (MOR). Noble metals have been widely studied as the most commonly used anode catalysts. However, high prices and limited reserves have severely hindered their further development. In addition, the active surface of Pt is susceptible to the poison of COads intermediate products, leading to the rapid loss of the catalytic activity due to blocked Pt sites. Considering the above problems, the design and development of low Pt or non-Pt nanocatalysts with an excellent antipoisoning ability have become very important. Transition metals have been widely used as promising substitutes for noble metal catalysts because of their abundant reserves, low price, and high catalytic activity. Among the transition metals studied, Ni, Cu, and Co have attracted sustained attention because of their high corrosion resistance. Owing to the ligand effect and synergistic effect, the addition of transition metals can effectively weaken the adsorption of COads intermediates on Pt sites. At the same time, non-noble transition metals are easy to form MOOH active species, which promote the oxidation of COads intermediates. Besides, methanol electrooxidation performance is closely related to the shape, structure, and composition of transition metals. From the principle of DMFC anode electrocatalysis, this review summarized the research progress of transition metal-based catalysts (transition metal-noble metal catalysts, transition metal catalysts, and self-supporting catalysts) in MOR. More importantly, the effects of the nanocatalyst composition, porous structure, high-index surface, crystal defects, and vertex enhancement on its electrochemical properties were emphasized. Finally, opportunities and challenges faced by transition metal-based electrocatalysts in DMFC were discussed.
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圖 1 酸性介質中的直接甲醇燃料電池（a），堿性介質中的直接甲醇燃料電池（b）
Figure 1. Direct methanol fuel cell in (a) an acidic medium and (b) a basic medium
圖 2 CuPt納米晶的（a）掃描電鏡和（b）透射電鏡圖像；（c）沿[111]帶軸的高分辨透射電鏡圖像(插圖：傅里葉變換圖像)；（d）高指數晶面{211}、{312}和{413}；（e）X射線衍射譜；（f）透射電鏡能譜[28]；（g）Ni0.20Pt0.80納米花的透射電鏡圖像，插圖：尺寸分布直方圖；（h）{111}面的高分辨電鏡圖像；（i）沿[011]軸觀察到的高分辨電鏡圖像，插圖：傅里葉變換圖像；沿（j）{111}和（k）{200}面原子層的線強度分布[30]
Figure 2. (a) Scanning electron microscopy and (b) transmission electron microscopy images of the CuPt nanocrystal; (c) high-resolution transmission electron microscopy image along the [111] zone axis (inset: fast Fourier transforms pattern); (d) high-index surface {211}, {312}, and {413}; (e) X-ray diffraction pattern and (f) transmission electron microscopy energy-dispersive X-ray spectroscopy [28]; (g) transmission electron microscopy image of Ni0.20Pt0.80 nanoflowers; inset: size distribution histogram; (h) high-resolution transmission electron microscopy image with {111} facets; (i) high-resolution transmission electron microscopy image viewed along the [011] axis (inset: fast Fourier transforms pattern); line intensity curves along the atomic layers of (j) {111} and (k) {200} facets[30]
圖 4 （a）PtCu RNF和Co-PtCu RNF形成過程示意圖；（b）催化劑在0.1 mol·L?1 HClO4 + 1 mol·L?1 CH3OH溶液中的循環伏安曲線；（c）加速耐久性實驗前后甲醇氧化反應的質量活性[41]
Figure 4. (a) Schematic of forming PtCu RNF and Co-PtCu RNF; (b) CVs of catalysts in 0.1 mol·L?1 HClO4 + 1 mol·L?1 CH3OH solution; (c) mass activity for the methanol oxidation reaction before and after accelerated durability tests[41]
圖 6 （a）Ni和Cu的高角環形暗場像-掃描透射電子圖像以及元素分布圖像；（b）Cu/NiCu NWs?220的能譜線掃描；（c）催化劑在1.55 V (vs RHE)下的質量電流密度；（d）甲醇在Cu/NiCu NWs表面的氧化機理[45]
Figure 6. (a) HAADF-STEM image and elemental mapping images for Cu and Ni; (b) EDS line scan profile for Cu/NiCu NWs?220; (c) mass current densities at 1.55 V (vs RHE) for the prepared catalysts; (d) methanol oxidation mechanism on the surface of Cu/NiCu NWs[45]
圖 8 （a）甲醇在Pt?CoSe?x/NiSe?nrs/NF上的氧化機理說明；（b）樣品在1 mol·L?1 KOH + 1 mol·L?1 CH3OH溶液中的循環伏安曲線；（c）CO剝離曲線[53]；（d）NF/Co3O4/NiCo2O4的掃描電鏡圖像；（e, f）樣品在1 mol·L?1 KOH + 0.5 mol·L?1 CH3OH溶液中10 MPa壓力前后的循環伏安和計時電流曲線[54]
Figure 8. (a) Mechanism illustration of the methanol oxidation on Pt?CoSe?x/NiSe?nrs/NF; (b) CV curves of prepared samples in 1 mol·L?1 KOH + 1 mol·L?1 CH3OH; (c) CO-stripping curves[53]; (d) scanning electron microscopy image of NF/Co3O4/NiCo2O4; (e) CV and (f) CA curves of samples before and after 10 MPa in 1 mol·L?1 KOH + 0.5 mol·L?1 CH3OH[54]
表 1 不同PtM二元催化劑電催化性能的比較
Table 1. Electrocatalytic performance comparison of different PtM binary catalysts
Electrocatalysts Area activity/ (mA·cm?2) Mass activity/ (mA·mg?1) Scanning rate/
(mV·s?1)Condition Cu@CuPt[28] 5.2 2284.5 50 0.5 mol·L?1 H2SO4 + 1 mol·L?1 CH3OH PtCu[31] 34.81 NR 50 0.5 mol·L?1 H2SO4 + 1 mol·L?1 CH3OH Pt32Cu68[32] NR 707 50 0.5 mol·L?1 H2SO4 + 0.5 mol·L?1 CH3OH CuPt3[33] 2.8 634.78 50 0.5 mol·L?1 H2SO4 + 0.5 mol·L?1 CH3OH Amorphous CuPt[34] 7.8 373.7 10 0.1 mol·L?1 HClO4 + 0.5 mol·L?1 CH3OH PtCu NCs[37] 2.88 1550 50 0.1 mol·L?1 HClO4 + 1 mol·L?1 CH3OH Pt34.5Cu65.5[38] 4.12 1430 50 0.1 mol·L?1 H2SO4 + 0.5 mol·L?1 CH3OH Pt71Co29[39] 2.51 666.23 50 0.1 mol·L?1 H2SO4 + 0.5 mol·L?1 CH3OH Pt95Co5[40] 2.13 491.4 50 0.5 mol·L?1 H2SO4 + 1 mol·L?1 CH3OH Ni0.2Pt0.8[30] NR 2200 50 0.5 mol·L?1 H2SO4 + 1 mol·L?1 CH3OH Pt-Ni-P MNCs[35] 2.28 1220 50 0.5 mol·L?1 H2SO4 + 1 mol·L?1 CH3OH Note：NR is “not report”. 
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