Metal-organic frameworks (MOFs) and MOF-derived nanostructures are recently emerging as promising catalysts for electrocatalysis applications. Herein, 2D MOFs nanosheets decorated with Fe-MOF nanoparticles are synthesized and evaluated as the catalysts for water oxidation catalysis in alkaline medium. A dramatic enhancement of the catalytic activity is demonstrated by introduction of electrochemically inert Fe-MOF nanoparticles onto active 2D MOFs nanosheets. In the case of active Ni-MOF nanosheets (Ni-MOF@Fe-MOF), the overpotential is 265 mV to reach a current density of 10 mA cm −2 in 1 m KOH, which is lowered by ≈100 mV after hybridization due to the 2D nanosheet morphology and the synergistic effect between Ni active centers and Fe species. Similar performance improvement is also successfully demonstrated in the active NiCo-MOF nanosheets. More importantly, the real catalytic active species in the hybrid Ni-MOF@Fe-MOF catalyst are unraveled. It is found that, NiO nanograins (≈5 nm) are formed in situ during oxygen evolution reaction (OER) process and act as OER active centers as well as building blocks of the porous nanosheet catalysts. These findings provide new insights into understanding MOF-based catalysts for water oxidation catalysis, and also shed light on designing highly efficient MOF-derived nanostructures for electrocatalysis.
Highly active, durable, and inexpensive nanostructured catalysts are crucial for achieving efficient and economical electrochemical water splitting. However, developing efficient approaches to further improve the catalytic ability of the well-defined nanostructured catalysts is still a big challenge. Herein, we report a facile and universal cation-exchange process for synthesizing Fe-doped Ni(OH)2 and Co(OH)2 nanosheets with enriched active sites toward enhanced oxygen evolution reaction (OER). In comparison with typical NiFe layered double hydroxide (LDH) nanosteets prepared by the conventional one-pot method, Fe-doped Ni(OH)2 nanosheets evolving from Ni(OH)2 via an Fe3+/Ni2+ cation-exchange process possess nanoporous surfaces with abundant defects. Accordingly, Fe-doped Ni(OH)2 nanosheets exhibit higher electrochemical active surface area (ECSA) and improved surface wettability in comparison to NiFe LDH nanosheets and deliver significantly enhanced catalytic activity over NiFe LDH. Specifically, a low overpotential of only 245 mV is required to reach a current density of 10 mA cm-2 for Ni0.83Fe0.17(OH)2 nanosheets with a low Tafel slope of 61 mV dec-1, which is greatly decreased in comparison with those of NiFe LDH (310 mV and 78 mV dec-1). Additionally, this cation-exchange process is successfully extended to prepare Fe-doped Co(OH)2 nanosheets with improved catalytic activity for oxygen evolution. The results suggest that this cation-exchange process should have great potential in the rational design of defect-enriched catalysts toward high-performance electrocatalysis.
Energy storage and conversion technologies are vital to the efficient utilization of sustainable renewable energy sources. Rechargeable lithium‐ion batteries (LIBs) and the emerging sodium‐ion batteries (SIBs) are considered as two of the most promising energy storage devices, and electrocatalysis processes play critical roles in energy conversion techniques that achieve mutual transformation between renewable electricity and chemical energies. It has been demonstrated that nanostructured metal chalcogenides including metal sulfides and metal selenides show great potential for efficient energy storage and conversion due to their unique physicochemical properties. In this feature article, the recent research progress on nanostructured metal sulfides and metal selenides for application in SIBs/LIBs and hydrogen/oxygen electrocatalysis (hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction) is summarized and discussed. The corresponding electrochemical mechanisms, critical issues, and effective strategies towards performance improvement are presented. Finally, the remaining challenges and perspectives for the future development of metal chalcogenides in the energy research field are proposed.
Interface engineering is one feasible and effective approach to minimize the interfacial nonradiative recombination stemming from interfacial defects, interfacial residual stress, and interfacial energy level mismatch. Herein, a novel and effective steric-hindrance-dependent buried interface defect passivation and stress release strategy is reported, which is implemented by adopting a series of adamantane derivative molecules functionalized with CO (i.e., 2-adamantanone (AD), 1-adamantane carboxylic acid (ADCA), and 1-adamantaneacetic acid (ADAA)) to modify SnO 2 /perovskite interface. All modifiers play a role in passivating interfacial defects, mitigating interfacial strain, and enhancing device performance. The steric hindrance of chemical interaction between CO in these molecules and perovskites as well as SnO 2 is determined by the distance between CO and bulky adamantane ring, which gradually decreases from AD, ADCA, and ADAA. The experimental and theoretical evidences together confirmed steric-hindrance-dependent defect passivation effect and interfacial chemical interaction strength. The interfacial chemical interaction strength, defect passivation effect, stress release effect and thus device performance are negatively correlated with steric hindrance. Consequently, the ADAA-modified device achieves a seductive efficiency up to 23.18%. The unencapsulated devices with ADAA maintain 81% of its initial efficiency after aging at 60 °C for 1000 h.
We report on the demonstration of photodetectors based on large scale two-dimensional molybdenum disulfide (MoS2) transition metal dichalcogenides. Excellent film uniformity and precise control of the MoS2 thickness down to a monolayer (~0.75nm) were achieved by magnetron sputtering synthesis approach. In particular, the photodetectors integrated with five MoS2 monolayers exhibit a high photoresponsivity of 1.8 A/W, an external quantum efficiency exceeding 260%, and a photodetectivity of ~5 x 10(8) Jones for a wavelength of 850 nm, surpassing the performance of mechanically exfoliated based photodetectors.
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