Nitrogen-doped Carbon Thin Films Research Articles

Carbon-Based Electrode Materials for Electrocatalytic Transformations

Industrial processes for the synthesis of chemicals and fuels utilise selective hydrogenation reactions. The need for high temperatures and high pressure of H2 makes these reactions energy intensive and only viable on a large scale, requiring expensive transport of materials. Electrocatalytic hydrogenation (ECH) could potentially bypass these limitations, running at ambient conditions and generating the adsorbed hydrogen in-situ. The interest in new electrocatalyst materials increased in recent years, as ECH offers a synthetic route for fuels and value-added chemicals with a reduced carbon footprint. The development of new low-cost catalyst materials will be paramount for the integration of ECH into economic activities.In this work we focus on heteroatom-modified carbon based electrode materials for the ECH. Carbon materials possess a list of beneficial properties for electrochemical applications: they are widely available, environmentally benign, stable at cathodic potentials and can be tailored towards specific applications. One way of tailoring is to dope the carbon with heteroatoms like nitrogen.Nitrogen-doped carbon thin films have been synthesised using sputter deposition followed by an annealing process, to control graphitisation and nitrogen distribution of the carbon material. These model electrodes were investigated by themselves and as supports for thin nanoparticle films of MoS2 in the ECH and the hydrogen evolution reaction (HER), as the Volmer step of the HER is needed in the ECH. This allowed us to understand the influence of nitrogen moieties on reduction rates in the absence of morphological effects. The results suggest possible strategies for developing electrocatalysts for the ECH based on functional carbons.[1] Orella, M.J.; Román-Leshkov, Y.; Brushett, F.R., Emerging opportunities for electrochemical processing to enable sustainable chemical manufacturing. Current Opinion in Chemical Engineering 2018, 20, 159–167.[2] Behan, J. A.; Stamatin, S. N.; Hoque, M. K.; Ciapetti, G.; Zen, F.; Esteban-Tejeda, L.; Colavita, P. E., Combined Optoelectronic and Electrochemical Study of Nitrogenated Carbon Electrodes. The Journal of Physical Chemistry C 2017, 121 (12), 6596-6604.[3] Nolan, H.; Schröder, C.; Brunet-Cabré, M.; Pota, F.; McEvoy, N.; McKelvey, K.; Perova, T. S.; Colavita, P. E., MoS2/carbon heterostructured catalysts for the hydrogen evolution reaction: N-doping modulation of substrate effects in acid and alkaline electrolytes. Carbon 2023, 202, 70-80.

1T-Phase molybdenum sulfide/cobalt oxide nanopillars hybrid nanostructure coupled with nitrogen-doped carbon thin-film as high efficiency electrocatalyst for oxygen evolution

High efficient and durable catalysts are always needed to lower the kinetic barriers as well as prolong the service life associated with oxygen evolution reaction (OER). Herein, a sequential synthetic strategy is considered to prepare a hierarchical nanostructure, in which each component can be configured to achieve their full potential so that endows the resulting nanocatalyst a good overall performance. In order to realize this, well-organized cobalt oxide (Co3O4) nanopillars are firstly grown onto ultrathin 1T-molybdenum sulfide (1T-MoS2) to obtain high surface area electrocatalyst, providing electron transfer pathways and structural stability. After that, zeolitic imidazolate framework-67 (ZIF-67) derived carbonization film is further in situ deposited on the surface of nanopillars to generate plentiful active sites, thereby accelerating OER kinetics. Based on the combination of different components, the electron transfer capability, catalytic activity and durability are optimized and fully implemented. The obtained nanocatalyst (defined as 1T-MoS2/Co3O4/CN) exhibits the superior OER catalytic ability with the overpotential of 202 mV and Tafel slope of 57 mV·dec−1 at 10 mA·cm−2 in 0.1 M KOH, and good durability with a minor chronoamperometric decay of 9.15 % after 60,000 s of polarization.

Comparison and semiconductor properties of nitrogen doped carbon thin films grown by different techniques

Amorphous carbon nitride (a-CN x ) thin films have been synthesised by three different deposition techniques in an Ar/N 2 gas mixture and have been deposited by varying the percentage of nitrogen gas in the mixture (i.e. the N 2/Ar + N 2 ratio) from 0 to 10%. The variation of the electrical conductivity and the gap values of the deposited films versus the N 2/Ar + N 2 ratio were investigated in relation with their local microstructure. Film composition was analysed using Raman spectroscopy and optical transmission experiments. The observed variation of electrical conductivity and optical properties are attributed to the changes in the atomic bonding structures, which were induced by N incorporation, increasing both the sp 2 carbon content and their relative disorder. The low N content samples seem to be an interesting material to produce films with interesting properties for optoelectronic applications considering the facility to control the gas composition as a key parameter.

Nitrogen Doping in Carbon Nanotubes

Nitrogen doping of single and multi-walled carbon nanotubes is of great interest both fundamentally, to explore the effect of dopants on quasi-1D electrical conductors, and for applications such as field emission tips, lithium storage, composites and nanoelectronic devices. We present an extensive review of the current state of the art in nitrogen doping of carbon nanotubes, including synthesis techniques, and comparison with nitrogen doped carbon thin films and azofullerenes. Nitrogen doping significantly alters nanotube morphology, leading to compartmentalised 'bamboo' nanotube structures. We review spectroscopic studies of nitrogen dopants using techniques such as X-ray photoemission spectroscopy, electron energy loss spectroscopy and Raman studies, and associated theoretical models. We discuss the role of nanotube curvature and chirality (notably whether the nanotubes are metallic or semiconducting), and the effect of doping on nanotube surface chemistry. Finally we review the effect of nitrogen on the transport properties of carbon nanotubes, notably its ability to induce negative differential resistance in semiconducting tubes.