In recent years, there has been growing interest in the potential applications of carbon-based non-metallic catalysts in various fields, such as electrochemical energy storage, electrocatalysis, thermal catalysis, and photocatalysis, owing to their unique physical and chemical properties. Modifying carbon catalyst surfaces or incorporating non-metallic heteroatoms, such as nitrogen (N), phosphorus (P), boron (B), and sulfur (S), into the carbon structure has emerged as a promising approach to improve the catalytic performance. This method enables the adjustment of the electronic structure of the carbon catalyst's surface, leading to the formation of new active sites or the reduction of side reactions, ultimately enhancing the catalyst's performance. Here, the preparation methods for doped non-metallic heteroatom carbon catalysts have been systematically explored, encompassing techniques, such as impregnation, pyrolysis, chemical vapor deposition (CVD), and templating. Finally, the existing challenges in the application of non-metallic atomic catalysts have been discussed, insights into potential future development opportunities and new preparation methods of carbon catalysts in the future have been offered.
Coal tar pitch is a raw material that can be made from various carbon materials such as activated carbon, carbon fiber, and artificial graphite through heat treatment. In particular, it is an important raw material used as a binder and impregnated pitch when manufacturing carbon composite materials. In order to improve the physical properties of such a carbon composite material, the content of β-resin is an important factor. Although β-resin plays the role of a binder, it also corresponds to fixed carbon, so it can determine the physical properties after carbonization. In this study, we compared the physical properties of coal tar pitch various temperature ramping rate, and found through Py-GC/MS analysis that intermediate materials were generated by heteroatoms such as oxygen and nitrogen. MALDI-TOF/MS analysis revealed that these intermediate materials overlapped with the molecular weight region of β-resin. Therefore, the content of β-resin is in the following order: 430–5 (12.8 wt%), 430–10 (10.2 wt%), and 430–2 (6.3 wt%), and when 430–5 is used as a binder, the highest density appeared at 1.75 g/cm3. However, such intermediate materials undergo thermal decomposition even at temperatures above 900 °C. As a result, after carbonization, 430–5 had a density of 1.60 g/cm3, which was similar or lower than that of 430–2 (1.72 → 1.63 g/ cm3) and 430–10 (1.73 → 1.61 g/cm3). From these results, it is expected that if the heteroatom content is distributed in an appropriate amount and the heating rate is well controlled, it will be possible to maintain a high density even after carbonization while ensuring a high beta-resin content.
Metal-free N–S- and N–P-doped nanocarbon (SCNP and PCNP) electrocatalysts prepared through sustainable microwaveassisted synthesis using hemigraphis alternata plant leaves. The prepared heteroatom-doped nanocarbon materials are active catalysts for the two-electron oxygen reduction reaction (ORR) to produce 65–70% of hydrogen peroxide. As evidenced from the XPS, most proportion of the doped heteroatoms contain the oxygen functional groups in the nanocarbons. These attributes are the critical factors to see the selective two-electron transfer ORR for the PCNP and SCNP. This approach shed light on the critical role of dual heteroatoms doping and the oxygen functionalities in nanocarbon towards the selectivity of ORR. We believe that this method would allow the preparation of heteroatom that contains oxygen functionalities. Our work paves a sustainable way of preparation of nanocarbon based ORR catalysts that are only selective for two-electron transfer process.
The detailed understanding of fluorescence emission processes is still unclear. This study demonstrates Aegle marmelos derived luminescent heteroatoms (N, Ca, K) doped carbon quantum dots (CQDs) using an economically and ecologically sustainable synthesis process without the necessity for any doping precursors due to its phytochemical, vitamin and mineral content. Carboxyl functionalization was done by adding lemon juice to the fruit extract. The morphological, physiochemical, compositional, crystallinity, and surface functional groups having heteroatom doped CQDs were analysed by HRTEM, EDX, XPS, XRD, FTIR etc. Besides, CQDs exhibited pH and solvent-dependent tuneable fluorescence characteristics. In fact, beyond pH 7.77, a protonation-deprotonation-driven red-shift was observed together with a decrease in the contribution of prominent peaks. Meanwhile, the features of solvatochromic fluorescence were examined in a range of aprotic and protic solvents with low and high polarity. Based on the studied Kamlet–Taft parameters and the obtained spectroscopic characterizations, a suitable fluorescence emission mechanism is provided. The observed solvatochromic fluorescence is thought to be caused by a combination of dipole moment polarisation, intramolecular charge transfer processes with or without H-bond stabilisation via the interaction of heteroatoms doped CQDs with solvent mediated by electron donation and acceptance from various surface functional groups such as hydroxyl, carboxyl with solvent molecules. Hence, this study is believed to promote the development of eco-tuneable fluorescent heteroatom doped CQDs and provide further insights into the fundamental fluorescence mechanisms, which include the relationship between morphology, surface properties and plausible quantum effects between CQDs and solvents.
A simple and one-pot synthetic procedure using two different sources has been demonstrated to prepare heteroatoms doped reduced graphene oxide such as nitrogen-doped reduced graphene oxide (N-RGO) and sulfur-doped reduced graphene oxide (S-RGO). The N-RGO has been hydrothermally synthesized using urea as nitrogen precursor, wherein the S-RGO has been synthesized using dimethyl sulfoxide (DMSO) as sulfur precursor. The successful N-doping, S-doping and other physicochemical properties of N-RGO and S-RGO have been confirmed with different spectroscopic and electrochemical techniques. The results indicated that doping into the graphene structure exhibits a high conductivity and a better transfer of charge. Moreover, heteroatoms doped graphene (N-RGO and S-RGO) and graphene-related materials (RGO) have been applied for the individual detection of uric acid (UA). Interestingly, the N-RGO exhibited a lower limit of detection (LOD, S/N = 3) of 2.7 10– 5 M for UA (10–1000 μM) compared with undoped RGO and S-RGO. Furthermore, the simultaneous detection of UA in the presence of Xanthine (XA) has been demonstrated a wide linear range of detection for UA: 10–1000 μM, with unchanged concentration of XA to be 200 μM, and exhibited a low limit of detection of 8.7 10− 5 M ( S∕N = 3) for UA. This modified sensor based on N-RGO has revealed a high selectivity and reproducibility thanks to its large surface area, high catalytic properties, and chemical structure. Indeed, the practical applicability of the proposed sensor has been evaluated in milk samples even in the presence of high concentrations of UA with satisfactory results.
Heteroatoms in situ-doped hierarchical porous hollow-activated carbons (HPHACs) have been prepared innovatively by pyrolyzation of setaria viridis combined with alkaline activation for the first time. The micro-morphology, pore structure, chemical compositions, and electrochemical properties are researched in detail. The obtained HPHACs are served as outstanding electrode materials in electrochemical energy storage ascribe to the particular hierarchical porous and hollow structure, and the precursor setaria viridis is advantage of eco-friendly as well as cost-effective. Electrochemical measurement results of the HPHACs electrodes exhibit not only high specific capacitance of 350 F g−1 at 0.2 A g−1, and impressive surface specific capacitance (Cs) of 49.9 μF cm−2, but also substantial rate capability of 68% retention (238 F g−1 at 10 A g−1) and good cycle stability with 99% retention over 5000 cycles at 5 A g−1 in 6 M KOH. Besides, the symmetrical supercapacitor device based on the HPHACs electrodes exhibits excellent energy density of 49.5 Wh kg−1 at power density of 175 W kg−1, but still maintains favorable energy density of 32.0 Wh kg−1 at current density of 1 A g−1 in 1-ethy-3-methylimidazolium tetrafluoroborate ( EMIMBF4) ionic liquid electrolyte, and the excellent cycle stability behaviour shows the nearly 97% ratio capacitance retention of the initial capacitance after 10,000 cycles at current density of 2 A g−1. Overall, the results indicate that HPHACs derived from setaria viridis have appealing electrochemical performances thus are promising electrode materials for supercapacitor devices and large-scale applications.