Nickel nanoparticles encapsulated in few-layer nitrogen-doped graphene (Ni@NC) are synthesized by using a Ni-based metal-organic framework as the precursor for high-temperature annealing treatment. The resulting Ni@NC materials exhibit highly efficient and ultrastable electrocatalytic activity toward the hydrogen evolution reaction and the oxygen evolution reaction as well as overall water splitting in alkaline environment.
Water splitting driven by sunlight or renewable resource-derived electricity has attracted great attention for sustainable production of hydrogen from water. Current research interest in this field is focused on the development of earth-abundant photo- or electrocatalytic materials with high activity and long-term stability for hydrogen and/or oxygen evolution reactions. Due to their unique properties and characteristics, carbon and related carbon-based materials show great potential to replace some of the existing precious metal catalysts in water splitting technology. This tutorial review summarizes the recent significant progress in the fabrication and application of metal-free carbonaceous materials as photo- or electrocatalysts for water splitting. Synthetic strategies and applications of various carbonaceous materials, including graphitic carbon nitride (g-C3N4), graphene, carbon nanotubes (CNTs) as well as other forms of carbon-containing materials, for electrochemical or photochemical water splitting are presented, accompanied by a discussion of the key scientific issues and prospects for the future development of metal-free photo- and electrocatalysts.
Developing high‐efficiency and low‐cost photocatalysts by avoiding expensive noble metals, yet remarkably improving H2 evolution performance, is a great challenge. Noble‐metal‐free catalysts containing Co(Fe)NC moieties have been widely reported in recent years for electrochemical oxygen reduction reaction and have also gained noticeable interest for organic transformation. However, to date, no prior studies are available in the literature about the activity of N‐coordinated metal centers for photocatalytic H2 evolution. Herein, a new photocatalyst containing g‐C3N4 decorated with CoP nanodots constructed from low‐cost precursors is reported. It is for the first time revealed that the unique P(δ−)Co(δ+)N(δ−) surface bonding states lead to much superior H2 evolution activity (96.2 µmol h−1) compared to noble metal (Pt)‐decorated g‐C3N4 photocatalyst (32.3 µmol h−1). The quantum efficiency of 12.4% at 420 nm is also much higher than the record values (≈2%) of other transition metal cocatalysts‐loaded g‐C3N4. It is believed that this work marks an important step toward developing high‐performance and low‐cost photocatalytic materials for H2 evolution.
engineering, that is, self-doping of vacancy in semiconductors,
has become a commonly used strategy to tune the photocatalytic performances.
However, there still lacks fundamental understanding of the role of
the vacancies in semiconductor materials. Herein, the g-C3N4 nanosheets with tunable nitrogen vacancies are prepared
as the photocatalysts for H2 evolution and CO2 reduction to CO. On the basis of both experimental investigation
and DFT calculations, nitrogen vacancies in g-C3N4 induce the formation of midgap states under the conduction band
edge. The position of midgap states becomes deeper with the increasing
of nitrogen vacancies. The g-C3N4 nanosheets
with the optimized density of nitrogen vacancies display about 18
times and 4 times enhancement for H2 evolution and of CO2 reduction to CO, respectively, as compared to the bulk g-C3N4. This is attributed to the synergistic effects
of several factors including (1) nitrogen vacancies cause the excitation
of electrons to midgap states below the conduction band edge, which
results in extension of the visible light absorption to photons of
longer wavelengths (up to 598 nm); (2) the suitable midgap states
could trap photogenerated electrons to minimize the recombination
loss of photogenerated electron–hole pairs; and (3) nitrogen
vacancies lead to uniformly anchored small Pt nanoparticles (1–2
nm) on g-C3N4, and facilitate the electron transfer
to Pt. However, the overintroduction of nitrogen vacancies generates
deeper midgap states as the recombination centers, which results in
deterioration of photocatalytic activities. Our work is expected to
provide new insights for fabrication of nanomaterials with suitable
vacancies for solar fuel generation.
The clustering of polycyclic aromatic hydrocarbon (PAH) molecules is investigated in the context of soot particle inception and growth using an isotropic potential developed from the benchmark PAHAP potential. This potential is used to estimate equilibrium constants of dimerisation for five representative PAH molecules based on a statistical mechanics model. Molecular dynamics simulations are also performed to study the clustering of homomolecular systems at a range of temperatures. The results from both sets of calculations demonstrate that at flame temperatures pyrene (C(16)H(10)) dimerisation cannot be a key step in soot particle formation and that much larger molecules (e.g. circumcoronene, C(54)H(18)) are required to form small clusters at flame temperatures. The importance of using accurate descriptions of the intermolecular interactions is demonstrated by comparing results to those calculated with a popular literature potential with an order of magnitude variation in the level of clustering observed. By using an accurate intermolecular potential we are able to show that physical binding of PAH molecules based on van der Waals interactions alone can only be a viable soot inception mechanism if concentrations of large PAH molecules are significantly higher than currently thought.
In this work, a one-pot solution method for direct synthesis of interconnected ultrafine amorphous NiFe-layered double hydroxide (NiFe-LDH) (<5 nm) and nanocarbon using the molecular precursor of metal and carbon sources is presented for the first time. During the solvothermal synthesis of NiFe-LDH, the organic ligand decomposes and transforms to amorphous carbon with graphitic nanodomains by catalytic effect of Fe. The confined growth of both NiFe-LDH and carbon in one single sheet results in fully integrated amorphous NiFe-LDH/C nanohybrid, allowing the harness of the high intrinsic activity of NiFe-LDH due to (i) amorphous and distorted LDH structure, (ii) enhanced active surface area, and (iii) strong coupling between the active phase and carbon. As such, the resultant NiFe-LDH/C exhibits superior activity and stability. Different from postdeposition or electrostatic self-assembly process for the formation of LDH/C composite, this method offers one new opportunity to fabricate high-performance oxygen evolution reaction and possibly other catalysts.
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.