过渡金属元素硫化物磷化物电

1、姓 名 导 师 杨婧 161102013 韩敏教授 过渡金属元素硫化物、磷化物的电 催化析氢 LOGO 2016.12.12 目录 1 背景 2 电析氢反应的机理及性能参数 3 合成方法 4 参考文献 1背景 背景 1 2 3 4 1 2 3 4 化石能源的日益枯竭 环境污染严重 水能、太阳能、风能等 可再生能源的局限性 氢气绿色无污染 Fig.1 Relationship between the M-H Adsorption Bonding Strength and the Exchange Current Densities in HER 2背景 2电析氢反应的机理及性能参数 Fig.2

2、Schematic diagram of a water electrolyzer Volmer-Tafel mechanism chemical desorption Volmer-Heyrovsky mechanism electrochemical desorption H2 H2 H H H H+ e+ H H+ e+ H H+ e+ H+ e+ 2 电析氢反应的机理及性能参数 2电析氢反应的机理及性能参数 onset potential 1 3 4 2 5 Tafel Slope Exchange Current Density Turnover Frequency Double L

3、ayer Capacitance C dl 起始电位 塔菲尔斜率 双电层电容 交换电流密度 转换效率 3合成方法 水热法 电化学沉积法 化学气相沉 积法 剥离法 溶剂热法 冶金法 4 DOI: 10.1039/c5ee03801d 亮点：通过水热合成法得到了长在碳布上的钼钨氧化物纳米线 并进一步磷化得到新颖多孔的钼钨磷化物纳米片，表现出了高 的电催化活性。 Figure.3 A schematic of the fabrication process of porous MoWP hybrid nanosheets on a carbon cloth. Fig.4 SEM and EDX el

4、emental mapping images of MoWO/CC (ac); SEM, HRTEM, TEM and EDX elemental mapping images of MoWP/CC (dh);and XRD patterns of MoWP/CC (i), the positions of the peaks belonging to the phases used in the Rietveld fit of the spectrum are indicated with vertical markers. Fig.5 (a) Polarization data for M

5、oWP/CC (iR corrected) in 0.50 M H2SO4 electrolyte at 2 mV s-1, along with plots of MoP/CC, WP2/CC and Pt/C/CC for comparison; (b) the corresponding Tafel plots of samples in (a); (c) stability of MoWP/CC in H2SO4 solution (0.5 M) at a scan rate of 100 mV s-1 before and after 4000 cycles between -0.2

6、 and +0.2 V (RHE); and (d) time dependence of catalytic current density during electrolysis for MoWP/CC at -100 mV (RHE). 亮点：用冶金法和电化学刻蚀两种方法合成了多孔、组分可 控制的双金属磷化物。 DOI: 10.1039/c6ee01109h Figure.6 (a) Schemical description of the fabrication process of free-standing nanoporous (Co1-xFex)2P. (b) The opti

7、cal photograph of a mother alloy ingot; (c) meltspun ribbon precursors; and (d) an as-prepared nanoporous (Co1-xFex)2P ribbon. Scalebar. Fig. 7 Microstructure characterization of three-dimensional nanoporous bimetallic phosphides. (a) SEM images of np-(Co0.52Fe0.48)2P. Inset shows the microstructure

8、 of cross-section of np-(Co0.52Fe0.48)2P. (b) X-ray diffraction pattern of the np-(Co1xFex)2P with various Co/Fe ratios. (c) XRD results at the (112) peak in the marked region of (b). The peak intensities of different samples were normalized to unity for comparison .Scale bars: (a) 500 nm, inset: 5

9、mm. DOI: 10.1021/acsami.6b07785 亮点：用电化学沉积得到了长在泡沫镍上的Co/CoP催化剂，这 种催化剂Co/CoP膜与基底之间有强的作用力减少了界面阻抗有 效的增加了电催化活性。 Figure.9 (A) XPS spectra in the Co 2p regions and (B) P2p regions of Co/CoP-NF catalyst; (C) HRTEM images of Co/CoP- NF; (D) XRD pattern of Co/CoP-NF. Figure.8 (A) Low- and (B) high- magnificati

10、on SEM images of Co/CoP-NF. (C) EDS elemental mapping images of elemental Co and P in Co/CoP-NFcatalyst. 亮点：用水热法合成了S、N、Co掺杂的石墨烯上负载硫化镍 钴气凝胶的催化剂，有效的提高了金属硫化物的循环性能。 DOI: 10.1002/advs.201600214 Figure.10 a) Schematic diagram of the synthesis of Ni-Co-S/SNGA; b) digital camera photo of the typical aerogel

11、 sample; and c) contact angle measurements before (left) and after (right) water dropping. Figure.11 a) XRD patterns of CoNi2S4/SNGA and CoNi2S4 reference pattern; b,c) low and highmagnification TEM images; and d) HRTEM of CoNi2S4/SNGA. 亮点：用化学插层剥离法得到了单层的 MoS2纳米晶，经过阳离子交换树脂的进 一步处理得到存在缺陷的MoS2纳米晶 K-MoS2

12、 乙醇 H2O超声 2h 单层 MoS2 NCs 阳离子交换树脂 S-Depletion MoS2 NCs Figure.11 Photographs of monolayered Mo-S NCs before and after S-depletion. Figure.12 (a) HRTEM image of the edge of initial NCs before S depletion. The inset is the related fast Fourier transform (FFT) pattern,confirming hexagonal and zigzag edg

13、e structures of the NC. (b,c) HRTEM images of the S-depleted MoS1.65 NCs. The FFT pattern (inset) in (c) reveals hexagonal crystal structure of the NC. (d) Raman spectrum of S-depleted MoS1.65 NCs. Figure.14 (a) Polarization curves and (b) Tafel plots (obtained from polarization curves) of bulk MoS2

14、, MoS2 NCs, S-depleted MoS1.65NCs, 4MoS1.65/EG catalysts, and Pt electrode. DOI: 10.1002/smll.201601168 亮点：用气相沉积法（CVD）将负载在碳纤维纳米线上的CoO 中的钴转移到了WS2纳米片上，表现出了好的电催化活性。 Figure.15 a) Schematic illustrating the transfer of cobalt atom from CoO NW grown on carbon fiber to WS2 nanosheet grown on W foil in a ty

15、pical two zone CVD furnace. b) The HER setup when the as-obtained ternary CoxW1xS2is used as electrocatalysts. WE = working electrode, RE = Reference electrode. Figure.16 a) Raman spectrum of WS2 and CoxW1xS2 nanosheets. High resolution XPS spectra of b) W 4f region, c) S 2p region, and d) Co 2p region of CoxW1xS2 nanosheets. Figure.17 Electr