Amorphous Nd-Ni-B/NF Rare Earth Composites: Preparation and HER Electrocatalytic Performance

doi:10.15541/jim20200450

Abstract

Abstract:

The amorphous nano-Nd-Ni-B rare earth (RE) alloy catalytic electrode on nickel foam (NF) was prepared by simple one-step electroless deposition method and served as a highly active hydrogen evolution reaction (HER) catalyst. Its microstructure and electrocatalytic HER performance were characterized. The results show that addition of Nd improved the electrocatalytic HER. The preparation conditions were optimized with neodymium nitrate of 3 g?L^-1, reaction temperature of 35 ℃ and reaction time of 1 h. The Nd-Ni-B/NF electrode requires an overpotential of only 180 mV to achieve the current density of 20 mA?cm^-2 in 1.0 mol?L^-1 KOH solution, and the corresponding Tafel slope is 117 mV?dec^-1. HER of Nd-Ni-B/NF catalyst is controlled by Volmer-Heyrovsky step. Moreover, the Nd-Ni-B/Nf shows superior electrochemical stability, 12 h chronoamperometry and 2000 sweeps of cyclic voltammetry with no obvious activity decay.

Key words: electroless deposition, Nd-Ni-B, amorphous nano, hydrogen evolution reaction, nickel foam

CLC Number:

TQ174

ZHU Yunna, CHEN Biqing, CHENG Tianshu, DU Chan, ZHANG Shimin, ZHAO Jing. Amorphous Nd-Ni-B/NF Rare Earth Composites: Preparation and HER Electrocatalytic Performance[J]. Journal of Inorganic Materials, 2021, 36(6): 637-644.

Figures/Tables 16

Fig. 1 Schematic illustration for fabrication procedure of Nd-Ni-B/NF electrocatalysts

Fig. 2 SEM images of (a) NF and (b,c) 3-NNB/NF, (d) EDX mappings of 3-NNB/NF

Fig. 3 (a) TEM and (b) HRTEM images of 3-NNB/NF with inset in (b) showing the corresponding SAED pattern

Fig. 4 XRD patterns of 0-NNB/NF and 3-NNB/NF powders

Fig. 5 (a) LSV curves, (b) overpotentials at 20 mA?cm-2, (c) Tafel curves (derived from (a)) and (d) exchange current densities (j0) derived from the Tafel curves of x-NNB/NF(x=0, 2, 3, 4, 5) and Pt/C electrodes; (e) CV curves of 3-NNB/NF electrode at different scan rates; (f) Coulomb curves of charge double-layer capacitance of x-NNB/NF(x=0, 2, 3, 4, 5) electrodes

Fig. 6 Nyquist plots of x-NNB/NF(x=0, 2, 3, 4, 5) electrodes towards HER with inset showing the corresponding equivalent circuit

Fig. 7 (a) LSV curves and (b) Tafel curves of NNB/NF-y(y=25, 35, 45, 55) electrodes

Fig. 8 (a-e) CV curves at different scan rates and Coulomb curves of charge double-layer capacitance for NNB/NF-y (y=25, 35, 45, 55) electrodes

Fig. 9 (a) I-t curve for NNB/NF-35 under 100 mV static overpotential for stability test 12 h; (b) Polarization curves of NNB/NF-35 before and after 2000 CV sweeps; (c) LSV curves and digital photos (insets) of NNB/NF-35 electrodes with different shapes; (d) Comparison of HER activities for different non-noble electrocatalytic materials in alkaline solution

Fig. S1 SEM images of x-NNB/NF(x=0, 2, 3, 4, 5)

Fig. S2 CV curves at different scan rates for x-NNB/NF(x=0, 2, 3, 4, 5)

Table S1 EIS parameters of x-NNB/NF(x=0, 2, 3, 4, 5) electrodes

Electrode	R_s/(Ω∙cm^-2)	R_P/(Ω∙cm^-2)	R_ct/(Ω∙cm^-2)
0-NNB/NF	0.195	1.573	1.578
2-NNB/NF	0.167	1.294	1.310
3-NNB/NF	0.152	1.261	1.279
4-NNB/NF	0.165	1.438	1.455
5-NNB/NF	0.166	1.536	1.543

Fig. S3 (a) SEM image and XRD pattern of 3-NNB/Cu-600 ℃; (b) LSV curves of 3-NNB/Cu and 3-NNB/Cu-600 ℃

Fig. S4 Faradaic efficiencies for HER catalyzed by NNB/NF-35 in 1.0 mol?L-1 KOH

Fig. S5 SEM images of NNB/NF-35(a) before and (b) after the HER measurement for 12 h

Table S2 Comparison of the electrocatalytic HER activity for representative nonprecious HER catalysts in 1.0 mol∙L-1 KOH electrolyte

Catalyst	Current density@Overpotential	Tafel slope/(mV∙dec^-1)	Ref.
Nd-Ni-B/NF	20 mA∙cm^-2@180 mV	117	This work
Ni-Co/RuO₂	50 mA∙cm^-2@180 mV	168.3	[1]
Ni-Fe-S/Ti	50 mA∙cm^-2@126 mV	269	[2]
V-Ni₂P NSAs/CC	10 mA∙cm^-2@85 mV	95	[3]
Ni-Fe-P	10 mA∙cm^-2@174.2 mV	142.9	[4]
Ni/NiS	10 mA∙cm^-2@230 mV	123	[5]
FeP Nanorod	10 mA∙cm^-2@218 mV	146	[6]
Ni_0.5Co_0.5/NC	10 mA∙cm^-2@282 mV	189	[7]
FeCoP Nanoarrays	10 mA∙cm^-2@175 mV	132	[8]
Ni₂P-NiSe₂	10 mA∙cm^-2@66 mV	72.6	[9]
Ni-Co-P/NF	10 mA∙cm^-2@85 mV	46	[10]

References 37

[1]	GAO Q, ZHANG W, SHI Z, et al. Structural design and electronic modulation of transition-metal-carbide electrocatalysts toward efficient hydrogen evolution. Advanced Materials, 2019,31(2):1802880. DOI URL
[2]	DUAN J, CHEN S, ORTÍZ-LEDÓN C A, et al. Phosphorus vacancies that boost electrocatalytic hydrogen evolution by two orders of magnitude. Angewandte Chemie-International Edition, 2020,59(21):8181-8186. DOI URL
[3]	WAN X K, WU H B, GUAN B Y, et al. Confining sub-nanometer Pt clusters in hollow mesoporous carbon spheres for boosting hydrogen evolution activity. Advanced Materials, 2020,32(7):1901349. DOI URL
[4]	NWANEBU E O, YAO Y, OMANOVIC S. The influence of Ir content in (Ni_0.4Co_0.6)₁-_xIr_x-oxide anodes on their electrocatalytic activity in oxygen evolution by acidic and alkaline water electrolysis. Journal of Electroanalytical Chemistry, 2020,865:114122. DOI URL
[5]	DONG X, YAN H, JIAO Y, et al. 3D hierarchical V-Ni-based nitride heterostructure as a highly efficient pH-universal electrocatalyst for the hydrogen evolution reaction. Journal of Materials Chemistry A, 2019,7(26):15823-15830. DOI URL
[6]	WANG H F, CHEN L, PANG H, et al. MOF-derived electrocatalysts for oxygen reduction, oxygen evolution and hydrogen evolution reactions. Chemical Society Reviews, 2020,49(5):1414-1448. DOI URL
[7]	BAYATSARMADI B, ZHENG Y, RUSSO V, et al. Highly active nickel-cobalt/nanocarbon thin films as efficient water splitting electrodes. Nanoscale, 2016,8(43):18507-18515. DOI URL
[8]	CHEN Z, QING H, ZHOU K, et al. Metal-organic framework-derived nanocomposites for electrocatalytic hydrogen evolution reaction. Progress in Materials Science, 2020,108:100618. DOI URL
[9]	PENG K, ZHOU J, GAO H, et al. Emerging one-/two-dimensional heteronanostructure integrating SiC nanowires with MoS₂ nanosheets for efficient electrocatalytic hydrogen evolution. ACS Applied Materials & Interfaces, 2020,12(17):19519-19529.
[10]	ZHANG P, WANG M, YANG Y, et al. Electroless plated Ni-B_x films as highly active electrocatalysts for hydrogen production from water over a wide pH range. Nano Energy, 2016,19:98-107. DOI URL
[11]	XU N, CAO G, CHEN Z, et al. Cobalt nickel boride as an active electrocatalyst for water splitting. Journal of Materials Chemistry A, 2017,5(24):12379-12384. DOI URL
[12]	SHI J L, SHENG M Q, WU Q, et al. Preparation of electrode materials of amorphous Co-W-B/carbon cloth composite and their electro-catalytic performance for electrolysis of water. Chinese Journal of Materials Research, 2020,34(4):263-271.
[13]	GAO W, WEN D, HO J C, et al. Incorporation of rare earth elements with transition metal-based materials for electrocatalysis: a review for recent progress. Materials Today Chemistry, 2019,12:266-281. DOI URL
[14]	RÖßNER L, ARMBRÜSTER M. Electrochemical energy conversion on intermetallic compounds: a review. ACS Catalysis, 2019,9(3):2018-2062. DOI URL
[15]	WU G, LI N, DAI C S, et al. Electrochemical preparation and characteristics of Ni-Co-LaNi₅ composite coatings as electrode materials for hydrogen evolution. Materials Chemistry and Physics, 2004,83:307-314. DOI URL
[16]	ZHU Y, CHEN B, CHENG T, et al. Deposit amorphous Ni-Co-B-RE (RE=Ce, Gd and Nd) on nickel foam as a high performance and durable electrode for hydrogen evolution reaction. Journal of Electroanalytical Chemistry, 2020,878:114552. DOI URL
[17]	ROSALBINO F, DELSANTE S, BORZONE G, et al. Electrocatalytic behaviour of Co-Ni-R (R=Rare earth metal) crystalline alloys as electrode materials for hydrogen evolution reaction in alkaline medium. International Journal of Hydrogen Energy, 2008,33(22):6696-6703. DOI URL
[18]	GAO Z, YANG Z, LI Y, et al. Improving the phase stability and cycling performance of Ce₂Ni₇-type RE-Mg-Ni alloy electrodes by high electronegativity element substitution. Dalton Transactions, 2018,47(46):16453-16460. DOI URL
[19]	WANG M F, XIAO D H, ZHOU P F, et al. Effects of rare earth yttrium on microstructure and properties of Mg-Al-Zn alloy. Journal of Alloys and Compounds, 2018,742:232-239. DOI URL
[20]	LI H, LI H, DAI W, et al. Preparation of the Ni-B amorphous alloys with variable boron content and its correlation to the hydrogenation activity. Applied Catalysis A: General, 2003,238(1):119-130. DOI URL
[21]	XIA W S, FAN Y, JIANG Y S, et al. Local surface state of amorphous NiP and NiB alloy catalysts. Applied Surface Science, 1996,103(1):1-9. DOI URL
[22]	JIN H, LIU X, JIAO Y, et al. Constructing tunable dual active sites on two-dimensional C₃N₄@MoN hybrid for electrocatalytic hydrogen evolution. Nano Energy, 2018,53:690-697. DOI URL
[23]	ZHANG L, YIN J, WEI K, et al. Fabrication of hierarchical SrTiO₃@MoS₂ heterostructure nanofibers as efficient and low-cost electrocatalysts for hydrogen-evolution reactions. Nanotechnology, 2020,31(20):205604.
[24]	KHANI H, GRUNDISH N S, WIPF D O, et al. Graphitic-shell encapsulation of metal electrocatalysts for oxygen evolution, oxygen reduction, and hydrogen evolution in alkaline solution. Advanced Energy Materials, 2020,10(1):1903215.
[25]	WANG Y, ZOU K, WANG D, et al. Highly efficient hydrogen evolution from the hydrolysis of ammonia borane solution with the Co-Mo-B/NF nanocatalyst. Renewable Energy, 2020,154:453-460. DOI URL
[26]	SUN H, XU X, YAN Z, et al. Superhydrophilic amorphous Co-B-P nanosheet electrocatalysts with Pt-like activity and durability for the hydrogen evolution reaction. Journal of Materials Chemistry A, 2018,6(44):22062-22069. DOI URL
[27]	YU P, WANG F, SHIFA T A, et al. Earth abundant materials beyond transition metal dichalcogenides: a focus on electrocatalyzing hydrogen evolution reaction. Nano Energy, 2019,58:244-276. DOI URL
[28]	SHI J, SHENG M, WU Q, et al. Preparation of electrode materials of amorphous Co-W-B/carbon cloth composite and their electro-catalytic performance for electrolysis of water. Chinese Journal of Materials Research, 2020,34(4):263-271.
[29]	CHAUDHARI N, JIN H, KIM B, et al. Nanostructured materials on 3D nickel foam as electrocatalysts for water splitting. Nanoscale, 2017,9(34):12231-12247. DOI URL
[30]	ZHAO Y, ZHAO M, DING X, et al. One-step colloid fabrication of nickel phosphides nanoplate/nickel foam hybrid electrode for high-performance asymmetric supercapacitors. Chemical Engineering Journal, 2019,373:1132-1143. DOI URL
[31]	ZHU J, HU L, ZHAO P, et al. Recent advances in electrocatalytic hydrogen evolution using nanoparticles. Chemical Reviews, 2020,120(2):851-918. DOI URL
[32]	DU Z, JANNATUN N, YU D, et al. C60-decorated nickel-cobalt phosphide as an efficient and robust electrocatalyst for hydrogen evolution reaction. Nanoscale, 2018,10(48):23070-23079. DOI URL
[33]	WU Z Y, HU B C, WU P, et al. Mo₂C nanoparticles embedded within bacterial cellulose-derived 3D N-doped carbon nanofiber networks for efficient hydrogen evolution. NPG Asia Materials, 2016,8(7):e288-e288. DOI URL
[34]	VIJ V, SULTAN S, HARZANDI A M, et al. Nickel-based electrocatalysts for energy-related applications: oxygen reduction, oxygen evolution, and hydrogen evolution reactions. ACS Catalysis, 2017,7(10):7196-7225. DOI URL
[35]	SHARMA L, KHUSHWAHA H S, MATHUR A, et al. Role of molybdenum in Ni-MoO₂ catalysts supported on reduced graphene oxide for temperature dependent hydrogen evolution reaction. Journal of Solid State Chemistry, 2018,265:208-217. DOI URL
[36]	ANANTHARAJ S, NODA S. Amorphous catalysts and electrochemical water splitting: an untold story of harmony. Small, 2020,16(2):1905779. DOI URL
[37]	DENG B, ZHOU L, JIANG Z, et al. High catalytic performance of nickel foam supported Co₂P-Ni₂P for overall water splitting and its structural evolutions during hydrogen/oxygen evolution reactions in alkaline solutions. Journal of Catalysis, 2019,373:81-92. DOI URL