Nitrogen-doped graphene aerogel-supported ruthenium nanocrystals for pH-universal hydrogen evolution reaction

doi:10.1016/S1872-2067(21)63977-3

Abstract

Abstract:

The design and synthesis of high-performance and low-cost electrocatalysts for the hydrogen evolution reaction (HER), a key half-reaction in water electrolysis, are essential. Owing to their modest hydrogen adsorption energy, ruthenium (Ru)-based nanomaterials are considered outstanding candidates to replace the expensive platinum (Pt)-based HER electrocatalysts. In this study, we developed an adsorption-pyrolysis method to construct nitrogen (N)-doped graphene aerogel (N-GA)-supported ultrafine Ru nanocrystal (Ru-NC) nanocomposites (Ru-NCs/N-GA). The particle size of the Ru-NCs and the conductivity of the N-GA substrate can be controlled by varying the pyrolysis temperature. Optimal experiments reveal revealed that 10 wt% Ru-NCs/N-GA nanocomposites require overpotentials of only 52 and 36 mV to achieve a current density of 10 mA cm^-2 in 1 mol/L HClO₄ and 1 mol/L KOH electrolytes for HER, respectively, which is comparable to 20 wt% Pt/C electrocatalyst. Benefiting from the ultrafine size and uniform dispersion of the Ru-NCs, the synergy between Ru and the highly conductive substrate, and the anchoring effect of the N atom, the Ru-NCs/N-GA nanocomposites exhibit excellent activity and durability in the pH-universal HER, thereby opening a new avenue for the production of commercial HER electrocatalysts.

Key words: Water electrolysis, Graphene aerogels, Nitrogen doping, Ruthenium nanocrystals, Hydrogen evolution reaction

Yu Ding, Kai-Wen Cao, Jia-Wei He, Fu-Min Li, Hao Huang, Pei Chen, Yu Chen. Nitrogen-doped graphene aerogel-supported ruthenium nanocrystals for pH-universal hydrogen evolution reaction[J]. Chinese Journal of Catalysis, 2022, 43(6): 1535-1543.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63977-3

https://www.cjcatal.com/EN/Y2022/V43/I6/1535

Figures/Tables 11

Scheme 1. Preparation of Ru-NCs/N-GA nanocomposites.

Fig. 1. Physical characterization of Ru-NCs/N-GA-900 nanocomposites. (a) EDX spectrum; (b) TGA curve; (c) XRD spectrum; (d) Raman spectrum.

Fig. 2. Physical characterization of Ru-NCs/N-GA-900 nanocomposites. (a) SEM image; (b) high-resolution SEM image; (c) TEM image; (d) HRTEM image; (e) STEM-EDX elemental maps. Inset in (c): particle size distribution.

Fig. 3. XPS characterization of Ru-NCs/N-GA-900 nanocomposites. (a) XPS full spectrum; (b) C 1s spectrum; (c) N 1s spectrum; (d) Ru 3p spectrum.

Fig. 4. Physical characterization of GA-PAA-RuIII nanocomposites. (a) SEM image; (b) TEM image; (c) STEM-EDX elemental maps.

Fig. 5. Electrochemical performance of Ru-NCs/N-GA-900 nanocomposites and commercial 20 wt% Pt/C electrocatalyst in N2-saturated 1 mol/L KOH electrolyte. (a) LSV curves; (b) η10 values; (c) Tafel plots; (d) Nyquist plots at -0.01 V.

Table 1 Physical characterization data of Ru-NCs/N-GA-700, Ru-NCs/N-GA-900, Ru-NCs/N-GA-1100, and Ru-NCs/GA-900 nanocomposites.

Catalyst	N-doping	Particle size	Ru content (wt%)
Ru-NCs/N-GA-900	Yes	2.3 ± 0.5 nm	9.89
Ru-NCs/N-GA-1100	Yes	5 ± 0.6 nm	10.25
Ru-NCs/N-GA-700	Yes	3.5 ± 0.6 nm	10.22
Ru-NCs/GA-900	No	9 ± 0.9 nm	10.01

Fig. 6. Electrochemical performance of the Ru-NCs/N-GA-700, Ru-NCs/N-GA-900, Ru-NCs/N-GA-1100, and Ru-NCs/GA-900 nanocomposites and commercial 20 wt% Pt/C electrocatalyst in N2-saturated 1 mol/L KOH electrolyte. (a) LSV curves; (b) η10 values.

Fig. 7. Durability of Ru-NCs/N-GA-900 nanocomposites and 20 wt% Pt/C electrocatalyst. (a) LSV curves before and after 10000 CV cycles in 1 mol/L KOH electrolyte; (b) Chronopotentiometric curves at 10 mA cm-2.

Fig. 8. HER performance of the Ru-NCs/N-GA-700, Ru-NCs/N-GA-900, Ru-NCs/N-GA-1100, Ru-NCs/GA-900 nanocomposites and commercial 20 wt% Pt/C electrocatalyst. (a) LSV curves; (b) η10 values in N2-saturated 1 mol/L HClO4 electrolyte.

Table 2 HER performance of the Ru-based nanomaterials.

Catalyst	Electrolyte	η₁₀ (mV)	Year (Ref.)
Ru-NCs/N-GA-900	1 mol/L KOH	36	This work
RuTe₂ nanoparticles	1 mol/L KOH	45.1	2021[45]
RuNi nanoclusters	1 mol/L KOH	43	2021[46]
Macro/Meso RuC	1 mol/L KOH	58	2021[20]
PtRu alloy nanoparticles	1 mol/L KOH	59	2021[47]
Ru/C	1 mol/L KOH	62	2021[13]
Ru/carbon nanotubes	1 mol/L KOH	63	2021[12]
Ru/S-Ni₂P nanosheets	1 mol/L KOH	49	2021[48]
Ruthenium-doped CoP	1 mol/L KOH	51	2021[49]
RuP₂@C	1 mol/L KOH	78.9	2021[50]
Ru/NC-400	1 mol/L KOH	39	2021[51]
Ru-doped Ni-Fe oxide bone	1 mol/L KOH	100	2021[52]
20 wt% Ru/C	1 mol/L KOH	41	2021[53]
Ni_0.6Ru_0.4@C	1 mol/L KOH	91	2020[54]
Ru-ZIF-900	1 mol/L KOH	51.6	2020[55]
Ru-NiFe LDH	1 mol/L KOH	115.6	2020[56]
(Ru-Co) O_x nanoarrays	1 mol/L KOH	44.1	2020[57]
S-RuP nanoparticles	1 mol/L KOH	92	2020[58]
FeCoRuP arrays	1 mol/L KOH	43	2020[59]
PtRu bimetallic nanoparticles	1 mol/L KOH	95	2020[4]
Co-Ru-MoS₂ nanosheets	1 mol/L KOH	52	2020[60]
Ru_xP nanowires	1 mol/L KOH	41	2020[61]
Ni₅P₄-Ru nanoparticles	1 mol/L KOH	54	2020[62]
Ru-NCs/N-GA-900	1 mol/L HClO₄	52	This work
Ru-Ir nanoparticles	0.5 mol/L H₂SO₄	60	2021[63]
Ru nanoparticles	0.5 mol/L H₂SO₄	98	2021[63]
RuP₂@C	0.5 mol/L H₂SO₄	77.2	2021 [50]
Ru/NC-400	0.5 mol/L H₂SO₄	55	2021[51]
Ru boron-doped carbon	0.5 mol/L H₂SO₄	85	2020[64]
Ru single atoms/Ti₃C₂T_x	0.1 mol/L HClO₄	70	2020[65]
Ru-CeO₂ nanocomposite	0.5 mol/L H₂SO₄	74	2020[66]
Ru/Ni₃N-Ni	0.5 mol/L H₂SO₄	53	2020[36]
RuNi/carbon quantum dots	0.5 mol/L H₂SO₄	58	2020[67]

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