This study reports the preparation of a set of hybrid materials consisting of molybdenum disulfide (MoS 2 ) nanopatches on reduced graphene oxide (rGO) nanosheets by microwave specific heating of graphene oxide and molecular molybdenum precursors followed by thermal annealing in 3% H 2 and 97% Ar. The microwave process converts graphene oxide to ordered rGO nanosheets that are sandwiched between uniform thin layers of amorphous molybdenum trisulfide (MoS 3 ). The subsequent thermal annealing converts the intermediate layers into MoS 2 nanopatches with two-dimensional layered structures whose defect density is tunable by controlling the annealing temperature at 250, 325 and 600 °C, respectively. All three MoS 2 /rGO samples and the MoS 3 /rGO intermediate after the microwave step show a high Li-ion intercalation capacity in the initial 10 cycles (over 519 mA h g MoSx −1 , ∼3.1 Li + ions per MoS 2 ) which is attributed to the small MoS 2 nanopatches in the MoS 2 /rGO hybrids while the effect of further S-rich defects is insignificant. In contrast, the Zn-ion storage properties strongly depend on the defects in the MoS 2 nanopatches. The highly defective MoS 2 /rGO hybrid prepared by annealing at 250 °C shows the highest initial Zn-ion storage capacity (∼300 mA h g MoSx −1 ) and close to 100% coulombic efficiency, which is dominated by pseudocapacitive surface reactions at the edges or defects in the MoS 2 nanopatches. The fast fading in the initial cycles can be mitigated by applying higher charge/discharge currents or extended cycles. This study validates that defect engineering is critical for improving Zn-ion storage.
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Synthesis of defect-engineered molybdenum sulfides on reduced graphene oxide for enhanced hydrogen evolution reaction kinetics
Amorphous molybdenum sulfide (a-MoS3) is a promising non-precious electrocatalyst for hydrogen evolution reaction owing to the abundant defective active sites. Here in, we show a rapid microwave-assisted synthesis method to produce a-MoS3 catalysts on reduced graphene oxide (rGO) substrates. The a-MoS3 reported in this study comprise of two possible 1D chain-like structures, i.e., with molybdenum (IV) in Weber’s model and molybdenum (V) in Hibble’s model, unlike the polymeric cluster type a-MoS3 structures reported in literature. Thermal annealing of the microwave-prepared a-MoS3 produced a family of defect-engineered MoSx/rGO hybrids, from a-MoS3 to crystalline MoS2, which showed tunable HER activities. XPS analysis provided in-depth understanding of the compositional changes in MoSx/rGO with thermal annealing. The a-MoS3/rGO 250 (annealed at 250 ◦C) exhibited the highest HER catalytic activity among all the MoSx/rGO hybrids, with an overpotential of 208 mV at 10 mA/cm2, a low Tafel slope of 52 mV/decade, a high double layer capacitance of 3.7 mF/cm2 and a high TOF value of 0.43 H2/s per site at the HER overpotential of 208 mV. The excellent HER activity is attributed to both MoV and sulfur active sites. This study provides a controllable, scalable and rapid synthesis method to produce 1D chain-like a-MoS3 structures for HER electrocatalysis.
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- PAR ID:
- 10511119
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- International Journal of Hydrogen Energy
- Volume:
- 51
- Issue:
- PC
- ISSN:
- 0360-3199
- Page Range / eLocation ID:
- 1387 to 1396
- Subject(s) / Keyword(s):
- Molybdenum sulfide Hydrogen evolution reaction Electrocatalyst Defect engineering Hybrid materials
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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