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Nanomaterials 2020, 10, 1407 16 of 26 N-doping of CNHs (Figure 5). The so-formed hybrid electrocatalyst, pyrolyzed at 400 ◦C, exhibited excellent stability and good electrocatalytic OER activity, outperforming the commercial noble-metal catalyst and the state-of-the-art Ni-based catalysts [151–155], but also the Ni-based graphene and CNT-based hybrids [156]. Nanomaterials 2020, 10, x FOR PEER REVIEW 19 of 32 Figure 5. Schematic illustrations of the (a) synthetic route of N-CNH-Ni-MOF and its derivatives, and Figure 5. Schematic illustrations of the (a) synthetic route of N-CNH-Ni-MOF and its derivatives, and (b) polymerization of dopamine. Reproduced with permission from [150]. Copyright © American (b) polymerization of dopamine. Reproduced with permission from [150]. Copyright © American Chemical Society, 2020. 2.4. Other Electrocatalytic Reactions 2.4. Other Electrocatalytic Reactions The CNHs have been also implemented in the electrochemical CO2 reduction reaction (CO2RR). Chemical Society, 2020. The CNHs have been also implemented in the electrochemical CO2 reduction reaction (CO2RR). The CO2 is a very stable molecule and requires high overpotential to start its reduction reaction [157]. At The CO2 is a very stable molecule and requires high overpotential to start its reduction reaction [157]. the cathode, CO2 is electrochemically reduced to chemicals or fuels, while the selectivity of CO2RR can At the cathode, CO2 is electrochemically reduced to chemicals or fuels, while the selectivity of CO2RR be properly managed to produce formic acid as renewable fuel. In this frame, hybrid heterostructures can be properly managed to produce formic acid as renewable fuel. In this frame, hybrid were prepared by integrating Pd nanoparticles on oxidized CNHs stabilized by a TiO2 outer-shell heterostructures were prepared by integrating Pd nanoparticles on oxidized CNHs stabilized by a (Pd@TiO2/ox-CNHs) [158], according to Figure 6. The Pd@TiO2/ox-CNHs hybrid material, when TiO2 outer-shell (Pd@TiO2/ox-CNHs) [158], according to Figure 6. The Pd@TiO2/ox-CNHs hybrid fabricated and employed as electrode, showed significant activity toward formate formation at low material, when fabricated and employed as electrode, showed significant activity toward formate potential (~0.2 V vs. RHE), while hydrogen evolution was observed over time, as a product of the formation at low potential (~0.2 V vs. RHE), while hydrogen evolution was observed over time, as a catalytic decomposition of formic acid accumulating in the system. In this system, CNHs acted as a product of the catalytic decomposition of formic acid accumulating in the system. In this system, scaffold, guaranteeing the electrical wiring of the Pd-active sites, and thus, boosting charge mobility. CNHs acted as a scaffold, guaranteeing the electrical wiring of the Pd-active sites, and thus, boosting Although the bifunctional heterostructure showed high activity for generating formic acid, it also charge mobility. Although the bifunctional heterostructure showed high activity for generating formic acid, it also highly produced the CO intermediate. Moreover, the selectivity that the hybrid material showed toward formate formation was not as high compared to Sn or Bi metals [159,160].PDF Image | Carbon Nanohorn-Based Electrocatalysts for Energy Conversion
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