纳米八面体形FeP@PC的制备及催化析氢性能

doi:10.7503/cjcu20190047

摘要/Abstract

摘要：

以UIO-66为载体, 经过FeCl₃化学气相沉积、原位碳化和磷化及HF刻蚀等步骤制备了多孔FeP@PC催化剂. 利用X射线衍射仪、场发射透射电子显微镜、 X射线光电子能谱仪和气体吸附仪等对催化剂的结构、形貌和比表面积等进行了表征; 同时采用线性扫描伏安法和电化学阻抗谱等对其电化学性质进行了考察. 结果表明, FeP@PC保持了原UIO-66的八面体多孔结构, 比表面积为83 m ²/g; 仅需要过电位156 mV即可驱动电流密度10 mA/cm ², 塔菲尔斜率为84 mV/dec, 电荷转移电阻为44 Ω, 电化学活性表面积为13.9 mF/cm ²; 在持续电解12 h和循环1000次后, 催化剂的活性几乎没有衰减.

关键词: 磷化铁, 金属有机框架, 化学气相沉积, 原位磷化, 析氢反应

Abstract:

By using UIO-66 as the precursor, porous FeP@PC was prepared by chemical vapor deposition of FeCl₃, in-situ carbonization, phosphating and HF etching. The morphology, crystal structure, elemental composition and valence states of FeP@PC were characterized by field emission transmission electron microscopy(FETEM), X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and N₂ adsoption-desorption measurements. The results showed that FeP@PC maintained the original porous nano-octahedral structure of UIO-66 and had a high specific surface area of 83 m ²/g. For linear sweep voltammetry and electrochemical impedance spectroscopy measurements, the catalyst FeP@PC only needed overpotential of 156 mV to driven current density of 10 mA/cm ². Meanwhile, the Tafel slope, the electron-transfer resistance and the electrochemically active surface area of the catalyst were calculated to be 84 mV/dec, 44 Ω and 13.9 mF/cm ², respectively. In order to evaluate the durability and stability of the catalyst, 12 h-chronoamperometry and 1000-cycle cyclic voltammetry measurements were also conducted and no obvious activity decay was observed.

Key words: Iron phosphide, Metal-organic framework, Chemical vapor deposition(CVD), In situ phosphating, Hydrogen evolution reaction

中图分类号:

O646.51

TrendMD:

王文峰, 秦山, 张荣荣, 周盼盼, 杨庆华, 陈天云. 纳米八面体形FeP@PC的制备及催化析氢性能. 高等学校化学学报, 2019, 40(9): 1979.

WANG Wenfeng, QIN Shan, ZHANG Rongrong, ZHOU Panpan, YANG Qinghua, CHEN Tianyun. Preparation of UIO-66-based Porous Nano-octahedral FeP@PC for Efficient and Durable Hydrogen Evolution ^†. Chem. J. Chinese Universities, 2019, 40(9): 1979.

图/表 11

Scheme 1 Illustration of the synthetic route of the FeP@PC nano-octahedron

Fig.1 TEM(A) and SEM(B) images of UIO-66

Fig.2 XRD patterns(A) and TGA curve(B) of UIO-66

Fig.3 TEM images(A, B), SAED pattern(C) and HRTEM image(D) of FeP@PC (B) Local magnified image, the particles circled by red circles are FeP.

Fig.4 TEM image(A) and Fe(B), P(C), C(D) elemental mapping images of FeP@PC

Fig.5 EDS spectrum of FeP@PC

Fig.6 XRD patterns(A), Raman spectra(B), N2 adsorption-desorption isotherms(C) and BJH pore size distributions(D) of FeP@PC(a) and FeP@EC(b)

Fig.7 Survey(A), Fe2p(B), P2p(C) and C1s(D) XPS spectra of FeP@PC

Fig.8 LSV curves(A), three dimensional histograms(B), Tafel plots(C) and EIS(D) of different electrocatalysts Inset in (D) is the equivalent circuit used to fit the impedance spectra.

Fig.9 Electrochemical double-layer capacitance of FeP@EC and FeP@PC(A) and polarization curves of FeP@PC before and after 1000 CV sweeps(B) Inset in (B) was chronoamperometry curve.

Table 1 Summery of HER performance for various non-noble metal electrocatalysts in 0.5 mol/L H2SO4

Catalyst	Mass loading/ (mg·cm^-2)	η₀/mV	η₁₀/mV	Tafel slope/ (mV·dec^-1)	Ref.
FeP@PC	0.193	58	156	84.0	This work
Fe_xP@NPC	0.20		227	81.0	[7]
FeP SSs	0.57		66	45.0	[9]
HMFeP@C	0.72	25	115	56.0	[11]
MoP@PC	0.41	77	153	66.0	[15]
Ni₂P/C	0.20	98	189	113.2	[16]
Cu₃P@NPPC	0.29		89.0	76	[24]
Mo₂C	0.21		221	53.0	[25]
FeP NR	0.20	45	120	55.0	[26]
HNDCM-Co/CoP			135	64.0	[33]
Ni₅P₄-Ni₂P nanosheet	0.28	54	120.0	79.1	[34]
NiS nanoframe	1.00		94	115.0	[35]
Hydrogenated FeP	0.72		145	64.0	[36]
MoS₂			210	97.0	[37]
FeP/GA	0.32		150	65.0	[38]

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