Abstract:The electrocatalytic properties of some endohedral fullerenes for hydrogen evolution reactions (HER) were recently predicted by DFT calculations. Nonetheless, the experimental catalytic performance under realistic electrochemical environments of these 0D-nanomaterials have not been explored. Here, for the first time, we disclose the HER electrocatalytic behavior of seven M 3 N@2n (2n = 68, 78, and 80) fullerenes (Gd 3 N@I h (7)-C 80 , Y 3 N@I h (7)-C 80 , Lu 3 N@I h (7)-C 80 , Sc 3 N@I h (7)-C 80 , Sc 3 N@D 5h… Show more
“…Adsorption energy (E a ) of an adsorbed molecule is the energy, which has to be delivered to the adsorbed atom to be desorbed from the surface. Adsorption is a surface-based exothermic reaction that liberates an expressive amount of energy when gas is adsorbed on a solid surface 43 , 44 . Hence, declining the residual forces on the surface of the adsorbent.…”
Section: Resultsmentioning
confidence: 99%
“…Where the negative values of the adsorption energies calculated indicated an exothermic adsorption. Thus, molecular adsorption leads to accumulation of negative charge at the corresponding adsorption sites, depending on the interaction between the adsorbed H 2 and the systems of interest 60 . Figure 7 Structurally optimized structures of molecular hydrogen adsorption on the considered nanoclusters exhibiting the bond length of interest.…”
The utilization of nanostructured materials as efficient catalyst for several processes has increased tremendously, and carbon-based nanostructured materials encompassing fullerene and its derivatives have been observed to possess enhanced catalytic activity when engineered with doping or decorated with metals, thus making them one of the most promising nanocage catalyst for hydrogen evolution reaction (HER) during electro-catalysis. Prompted by these, and the reported electrochemical, electronic and stability advantage, an attempt is put forward herein to inspect the metal encapsulated, doped, and decorated dependent HER activity of C
24
engineered nanostructured materials as effective electro-catalyst for HER. Density functional theory (DFT) calculations have been utilized to evaluate the catalytic hydrogen evolution reaction activity of four proposed bare systems: fullerene (C
24
), calcium encapsulated fullerene (Ca
enc
C
24
), nickel-doped calcium encapsulated fullerene (Ni
dop
Ca
enc
C
24
), and silver decorated nickel-doped calcium encapsulated (Ag
dec
Ni
dop
Ca
enc
C
24
) engineered nanostructured materials at the TPSSh/GenECP/6-311+G(d,p)/LanL2DZ level of theory. The obtained results divulged that, a potential decrease in energy gap (E
gap
) occurred in the bare systems, while a sparing increase was observed upon adsorption of hydrogen onto the surfaces, these surfaces where also observed to maintain the least E
H–L
gap while the Ag
dec
Ni
dop
Ca
enc
C
24
surface exhibited an increased electrocatalytic activity when compared to others. The results also showed that the electronic properties of the systems evinced a correspondent result with their electrochemical properties, the Ag-decorated surface also exhibited a proficient adsorption energy
and Gibb’s free energy (ΔG
H
) value. The engineered Ag-decorated and Ni-doped systems were found to possess both good surface stability and excellent electro-catalytic property for HER activities.
“…Adsorption energy (E a ) of an adsorbed molecule is the energy, which has to be delivered to the adsorbed atom to be desorbed from the surface. Adsorption is a surface-based exothermic reaction that liberates an expressive amount of energy when gas is adsorbed on a solid surface 43 , 44 . Hence, declining the residual forces on the surface of the adsorbent.…”
Section: Resultsmentioning
confidence: 99%
“…Where the negative values of the adsorption energies calculated indicated an exothermic adsorption. Thus, molecular adsorption leads to accumulation of negative charge at the corresponding adsorption sites, depending on the interaction between the adsorbed H 2 and the systems of interest 60 . Figure 7 Structurally optimized structures of molecular hydrogen adsorption on the considered nanoclusters exhibiting the bond length of interest.…”
The utilization of nanostructured materials as efficient catalyst for several processes has increased tremendously, and carbon-based nanostructured materials encompassing fullerene and its derivatives have been observed to possess enhanced catalytic activity when engineered with doping or decorated with metals, thus making them one of the most promising nanocage catalyst for hydrogen evolution reaction (HER) during electro-catalysis. Prompted by these, and the reported electrochemical, electronic and stability advantage, an attempt is put forward herein to inspect the metal encapsulated, doped, and decorated dependent HER activity of C
24
engineered nanostructured materials as effective electro-catalyst for HER. Density functional theory (DFT) calculations have been utilized to evaluate the catalytic hydrogen evolution reaction activity of four proposed bare systems: fullerene (C
24
), calcium encapsulated fullerene (Ca
enc
C
24
), nickel-doped calcium encapsulated fullerene (Ni
dop
Ca
enc
C
24
), and silver decorated nickel-doped calcium encapsulated (Ag
dec
Ni
dop
Ca
enc
C
24
) engineered nanostructured materials at the TPSSh/GenECP/6-311+G(d,p)/LanL2DZ level of theory. The obtained results divulged that, a potential decrease in energy gap (E
gap
) occurred in the bare systems, while a sparing increase was observed upon adsorption of hydrogen onto the surfaces, these surfaces where also observed to maintain the least E
H–L
gap while the Ag
dec
Ni
dop
Ca
enc
C
24
surface exhibited an increased electrocatalytic activity when compared to others. The results also showed that the electronic properties of the systems evinced a correspondent result with their electrochemical properties, the Ag-decorated surface also exhibited a proficient adsorption energy
and Gibb’s free energy (ΔG
H
) value. The engineered Ag-decorated and Ni-doped systems were found to possess both good surface stability and excellent electro-catalytic property for HER activities.
“…In a pioneering work, Santiago and colleagues disclose for the first time the underlying factors that govern the HER electrocatalytic behavior of seven M 3 N@C 2 n (2 n = 68, 78, and 80) fullerenes using an elegant combination of experimental and theoretical techniques. [ 103 ] The role of the metal, symmetry, number of carbon atoms, and non‐IPR sites towards the efficient production of molecular hydrogen of Gd 3 N@ I h (7)‐C 80 , Y 3 N@ I h (7)‐C 80 , Lu 3 N@ I h (7)‐C 80 , Sc 3 N@ I h (7)‐C 80 , Sc 3 N@ D 5h (6)‐C 80 , Sc 3 N@ D 3h (5)‐C 78 , and Sc 3 N@ D 3 (6140)‐C 68 EFMs were thoroughly explored ( Figure 6 A). Remarkably, they concluded that the structural variations among the metallic clusters such as the nature of the metal, symmetries, and degree of pyramidalization do not fulfill a substantial role in their HER catalytic activities.…”
Section: Structural Properties Of Sacs and Aces Supported On Ld Nanom...mentioning
confidence: 99%
“…Adapted with permission. [ 103 ] Copyright 2020, American Chemical Society. D) Schematic diagram of the synthetic strategy for CNT@C 3 N 4 Fe&Cu NRR catalysts.…”
Section: Structural Properties Of Sacs and Aces Supported On Ld Nanom...mentioning
The fundamental relationship between structure and properties, which is called “structure‐property”, plays a vital role in the rational designing of high‐performance catalysts for diverse electrocatalytic applications. Low‐dimensional (LD) nanomaterials, including 0D, 1D, 2D materials, combined with low‐nuclearity metal atoms, ranging from single atoms to subnanometer clusters, are currently emerging as rising star nanoarchitectures for heterogeneous catalysis due to their well‐defined active sites and unbeatable metal utilization efficiencies. In this work, a comprehensive experimental and theoretical review is provided on the recent development of single atom and atomic cluster‐decorated LD platforms towards some typical clean energy reactions, such as water‐splitting, nitrogen fixation, and carbon dioxide reduction reactions. The upmost attractive structural properties, advanced characterization techniques, and theoretical principles of these low‐nuclearity electrocatalysts as well as their applications in key electrochemical energy devices are also elegantly discussed.
“…By comparison, cheap and earth-abundant metal-free electrocatalysts with high activity and good stability in acidic conditions are highly desired. Carbon nanomaterial is widely used as electrocatalysts due to their chemical stability and good conductivity [37][38][39][40][41][42]. Graphene, the typical carbon nanomaterial with twodimensional structure, has been demonstrated to facilitate the electrochemical reduction of nitrate into nitrite [43], which is regarded as the rate-determining step in the entire process of nitrate reduction [44][45][46][47].…”
N-doped graphene samples with different N species contents were prepared by a two-step synthesis method and evaluated as electrocatalysts for the nitrate reduction reaction (NORR) for the first time. In an acidic solution with a saturated calomel electrode as reference, the pyridinic-N dominant sample (NGR2) had an onset of 0.932 V and a half-wave potential of 0.833 V, showing the superior activity towards the NORR compared to the pyrrolic-N dominant N-doped graphene (onset potential: 0.850 V, half-wave potential: 0.732 V) and the pure graphene (onset potential: 0.698 V, half-wave potential: 0.506 V). N doping could significantly boost the NORR performance of N-doped graphene, especially the contribution of pyridinic-N. Density functional theory calculation revealed the pyridinic-N facilitated the desorption of NO, which was kinetically involved in the process of the NORR. The findings of this work would be valuable for the development of metal-free NORR electrocatalysts.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
