Additional doping of phosphorus into polypyrrole functionalized nitrogenous carbon nanotubes as novel metal-free oxygen reduction electrocatalyst in alkaline solution

Novel phosphorus-doped polypyrrole functionalized nitrogenous carbon nanotubes (P/NCNTs) was developed for the first time as metal-free electrocatalyst for enhancing the oxygen reduction reaction (ORR) activity in alkaline medium. The P/NCNTs was successfully synthesized by pyrolyzing PPy and triphenylphosphane (TPP) under N₂, using pyrrole as carbon and nitrogen precursors, TPP as phosphorus precursor. Various characterizations such as transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectra, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) reveal that the P/NCNTs material has covalently bound P atoms with carbon framework, which can introduce defect sites and can induce uneven charge distribution. Moreover, the content of pyridine N increased after P-doping, which is of great significance in improving the ORR activity. The electrochemical behavior of the resultant material shows that the P/NCNTs has much enhanced electroactivity and better stability for ORR. Additionally, a direct four-electron pathway occurred efficiently on P/NCNTs modified electrode. These enhanced performances indicate that P/NCNTs catalyst may be an excellent cathode catalyst for ORR.     

A noble silver nanoflower on nitrogen doped carbon nanotube for enhanced oxygen reduction reaction

An electrodeposition-approach for the synthesis of silver nanoflowers (AgNFs) on nitrogen doped carbon nanotubes (NCNTs) for the oxygen reduction reaction (ORR) in alkaline media has been developed. The as prepared material (NCNTs-AgNFs) has been characterized by various instrumental methods. The morphological analysis shows the unique rose-like AgNFs are placed onto the NCNTs with better dispersion. The higher population of AgNFs has also been observed onto NCNTs coated glassy carbon (GC) rather than bare GC plate. The X-ray photoelectron spectroscopy shows chemical reduction and N-doping has done successfully with the restoring sp² domain in carbon network. The electrocatalytic activities have been verified using cyclic voltammetry (CV) and hydrodynamic voltammetry techniques in 0.1 M KOH electrolyte. The resulting catalyst system, NCNT-AgNFs, surpasses the performance of Pt/C, in terms of a kinetic current density, better fuel selectivity and durability. It is also noteworthy that the NCNT-AgNFs exhibits a four-electron reduction pathway for ORR with lowering H₂O₂ yield. The admirable performance of NCNT-AgNFs catalyst along with higher durability holds great potential for application in various fuel cells as cathode catalyst.     

Nitrogen-doped carbon nanotubes with high activity for oxygen reduction in alkaline media

Nitrogen-doped carbon nanotubes (NCNTs) were prepared using a floating catalyst chemical vapour deposition method. The multiwalled NCNT contains 8.4 at% nitrogen and has a dimension of 100 nm in the diameter and 10-20 nm in the wall thickness. The catalytic activity and durability of the NCNTs towards oxygen reduction reaction (ORR) were evaluated by cyclic voltammetry (CV) and rotating ring-disk electrode (RRDE) techniques in KOH solution. In addition, the effects of KOH concentration on several ORR performance indicators of the NCNT catalyst, such as the number of electrons transferred, the diffusion-limiting current density, the onset and half-wave potentials, were also examined in electrolytes of various KOH concentrations, ranging from 0.1 to 12 M. Experimental results show that NCNTs exhibited comparable activity for ORR in alkaline electrolyte as compared with commercially available Pt/C catalyst, and much higher activity than commercial Ag/C catalysts. In addition, the NCNTs showed good stability from the potential cycling test, and the concentration of KOH had significant impact on the ORR performance indicators of the NCNT catalysts.     

Bio-inspired highly active catalysts for oxygen reduction reaction in alkaline electrolyte

A novel non-platinum oxygen reduction reaction (ORR) catalyst was synthesised by the pyrolysis of carbon-supported vitamin B12 under ammonia atmosphere. The resultant catalyst was characterised by transmission electron microscopy (TEM), scanning TEM (STEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS) analyses. Results demonstrated that the catalyst had a spherical structure. XPS revealed that the nitrogen configuration was changed after pyrolysis, and nitrogen species played a key role in catalysing the ORR. The catalyst exhibited an enhanced ORR activity than commercial 20% Pt/C in alkaline media. The catalyst had an electron transfer number of 3.9, which was very close to the ideal theoretical value of 4. Moreover, the catalyst displayed superior methanol tolerance to Pt/C in alkaline medium, demonstrating its potential application as a cost-effective catalyst for direct methanol alkaline fuel cells.     

Promotional effects of trace Ni on its dual-functional electrocatalysis of Co/N-doped carbon nanotube catalysts for ORR and OER

It is still a great challenge for developing efficient dual-functional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The electrocatalysts are critical to enhance the efficiency of metal-air cells and fuel cells. In this study, a one-pot vapor deposition method was used to realize the synchronously dope of N and Ni (trace) into Co/C to form Co–Ni (trace)/N-doped carbon nanotubes (Co–Ni (trace)/NCNTs). An interesting result is that injecting dicyandiamide (DCD) into Ni foam as a precursor led to the in situ formation of NCNTs, with synchronous doping of trace Ni into Co species. The cooperative effects of the Co–Ni (trace) and N-doped carbon nanotubes resulted in superior dual-functional electrocatalytic performance of Co–Ni (trace)/NCNTs for the ORR (half-wave potential E_1/2 vs. RHE: 0.83 V, electron transfer number n: 3.97) and OER (overpotential vs. RHE: 337 mV at 10 mA cm^?2, Tafel slope: 94.0 mV dec^?1). Moreover, the Co–Ni (trace)/NCNTs catalyst showed excellent stability during 20,000 s of durability testing for both ORR and OER. This study provides a feasible strategy for designing efficient nonnoble metal-catalysts for renewable energy conversion devices.     

Novel multi walled carbon nanotube based nitrogen impregnated Co and Fe cathode catalysts for improved microbial fuel cell performance

For application in a microbial fuel cell (MFC), transition metal and nitrogen co-doped nanocarbon catalysts were synthesised by pyrolysis of multi-walled carbon nanotubes (MWCNTs) in the presence of iron- or cobalt chloride and nitrogen source. For the physicochemical characterisation of the catalysts, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) was used. The results obtained by rotating disk electrode (RDE) method showed an extraordinary electrocatalytic activity of these catalysts towards oxygen reduction reaction (ORR) in neutral media, which was also confirmed by the MFC results. The Co-N-CNT and Fe-N-CNT cathode catalysts exhibited maximum power density of 5.1 W m^?3 and 6 W m^?3, respectively. Higher ORR activity and improved electric output in the MFC could be attributed to the formation of the active nitrogen-metal centers. All findings suggest that these materials can be used as potential cathode catalysts for ORR in MFC to replace expensive noble-metal based materials.     

Pd–Co nanoparticles decorated on different carbon based substrates as electrocatalyst for O2 reduction reaction

In this study, a facile process for the synthesis of bimetallic Pd–Co nanotubes on multi-walled carbon nanotubes (MWCNTs) and chemically reduced graphene oxide (rGO) is reported. The synthesized nanocatalysts are characterized by field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX). Catalysts are evaluated for the oxygen reduction reaction (ORR) in basic media. The electrocatalytic performance of Pd–Co supported on rGO and MWCNTs toward ORR is compared with bimetallic and single Pd nanoparticles decorated on Vulcan carbon (XC-72R) by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and rotating disk electrode (RDE) in 0.1 M NaOH solution. The specific electrochemical surface areas of Pd–Co supported on rGO is higher than the corresponding carbon-supported Pd nanoparticles (222.09 vs. 41.57 m² g⁻¹, respectively). The RDE results confirm that the final product of the oxygen reduction is water and the proposed main path is direct 4 electron transfer process with smooth transfer kinetic rate on the Pd–Co/rGO in comparison to Pd–Co/C. Furthermore, the lower charge transfer resistance of the particles in ORR process for the Pd–Co/rGO compared to single Pd/C catalyst, indicating it could be excellent candidate for ORR in alkaline media.     

Carbon nanotubes supported Fe-based compounds as the electrode catalyst for oxygen reduction reaction

An amorphous Fe-based catalyst supported on polypyrrole-modified carbon nanotubes is synthesized by a chemical method. The microstructure, surface composition and morphology are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The synthesized amorphous Fe-based catalyst is composed of amorphous FeOOH and microcrystalline Fe₂O₃. Compared with a crystalline FeOOH catalyst, the amorphous Fe-based catalyst demonstrates higher electrocatalytic activity toward the oxygen reduction reaction (ORR), due to its amorphous structure and large specific surface area. It is considered that amorphization of transition metal compounds could be one of the methods used to improve their catalytic activity toward the ORR.     

Cu-assisted induced atomic-level bivalent Fe confined on N-doped carbon concave dodecahedrons for acid oxygen reduction electrocatalysis

Atomically dispersed transition metals anchored on N-doped carbon have been successfully developed as promising electrocatalysts for acidic oxygen reduction reaction (ORR). Nonetheless, how to introduce and construct single-atomic active sites is still a big challenge. Herein, a novel concave dodecahedron catalyst of N-doped carbon (FeCuNC) with well confined atomically dispersed bivalent Fe sites was facilely developed via a Cu-assisted induced strategy. The obtained catalyst delivered outstanding ORR performance in 0.5 M H₂SO₄ media with a half-wave potential (E_1/2) of 0.82 V (vs reversible hydrogen electrode, RHE), stemming from the highly active bivalent Fe-N_x sites with sufficient exposure and accessibility guaranteed by the high specific surface area and curved surface. This work provides a simple but efficient metal-assisted induced strategy to tune the configurations of atomically dispersed active sites as well as microscopy structures of carbon matrix to develop promising PGM-free catalysts for proton exchange membrane fuel cell (PEMFC) applications.     

Pt nanoparticles sputter-deposited on TiO2/MWCNT composites prepared by atomic layer deposition: Improved electrocatalytic activity towards the oxygen reduction reaction and durability in acid media

Acid-treated multi-walled carbon nanotubes (MWCNTs) were decorated with TiO₂ using the atomic layer deposition (ALD) technique followed by uniform distribution of platinum nanoparticles (PtNPs) through magnetron sputtering. Surface analyses were performed by scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM) and X-ray photoelectron spectroscopy (XPS). Electrochemical decontamination and characterization of the Pt-TiO₂/MWCNT electrodes were carried out by CO stripping followed by cyclic voltammetry in acid media. The oxygen reduction reaction (ORR) was studied in O₂-saturated 0.05 M H₂SO₄ solution using the rotating disk electrode (RDE) method. Durability of the prepared catalysts was examined by repetitive potential cycling. Electrochemical data obtained was analyzed and compared to that of the commercial Pt/C catalyst. It was revealed that the Pt-TiO₂/MWCNT catalysts possess higher ORR activity and better durability as compared to that of the commercial Pt/C.     

Three-dimensional nitrogen-doped carbon nanotubes/carbon nanofragments complexes for efficient metal-free electrocatalyst towards oxygen reduction reaction

Heteroatom-doped carbon materials as one of the most promising oxygen reduction reaction (ORR) catalysts have attracted much attention. Rational design and exploration of suitable heteroatom-doped carbon materials greatly affects their ORR performance. Herein, we successfully prepared nitrogen-doped carbon nanotubes/carbon nanofragments (NCNT/CNF) complexes by a pyrolysis process using oxidized open-ended carbon nanotubes (OCNT)/oxidized carbon nanofragments (OCNF) hybrids as carbon precursors. The effect of carbon precursors on the synthesis of the corresponding nitrogen-doped carbon products was systematically investigated. The result showed the OCNT retained good conductivity, while the OCNF offered adequate structure defects for efficient post-doping. Benefiting from the co-merits of sole constitute, the obtained NCNT/CNF_1-15 (1–15 refers to the mass ratio) complexes possessed a typical three-dimensional architecture and much increased specific surface area, which facilitated reactant/electrolyte infiltration and ion/electron transfer. More importantly, they built the most optimized balance on ORR catalytic sites and conductivity. Thus, the NCNT/CNF_1-15 complexes showed much enhanced ORR performance. Clearly, our work provides a good guidance on the design of advanced heteroatom-doped carbon-based ORR catalysts.     

Ag nanoparticles on mesoporous carbon support as cathode catalyst for anion exchange membrane fuel cell

Silver nanocatalyst (40 wt%) is deposited on commercial mesoporous carbon support material (Ag/C) using two different wet chemical methods, to obtain high electrochemically active surface area. The catalyst materials are characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, thermogravimetric analysis and are evaluated toward the oxygen reduction reaction (ORR) in alkaline media employing the rotating disk electrode method. It is worth noting that the Ag/C leads to oxygen reduction through a direct four-electron pathway in alkaline medium. The silver catalyst on mesoporous carbon exhibits relatively higher mass activity for ORR (38 A g⁻¹) compared to that with Vulcan carbon (32 A g⁻¹) at −0.2 V vs SCE at room temperature. Anion exchange membrane fuel cell shows maximum power density of 310 mW cm⁻² with Ag/C cathode catalyst using H₂ and O₂ gases at 65% RH conditions at 65 °C.     

Mesoporous carbon supported nanoparticulated PdNi2: A methanol tolerant oxygen reduction electrocatalyst

The kinetics of the oxygen reduction reaction (ORR) of PdNi₂ nanoparticles supported on a high specific area mesoporous carbon (MC) and Vulcan carbon was studied in the presence and absence of methanol in acid media. The electrocatalysts, synthesized by chemical reduction of the metal chlorides with NaBH₄ in aqueous media were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The catalyst supported on MC has a higher degree of Ni alloying and a smaller particle size than that supported on Vulcan. The electrochemical characterizations by RDE and DEMS indicate that PdNi₂ supported on the high surface area MC exhibits higher catalytic activity for the ORR, very similar to that of Pd- and Pt-based alloys with the advantage of a very low noble metal loading. Moreover, the PdNi₂ supported on MC shows an excellent methanol tolerance in acid media. Thus, this novel combination catalyst/support would be a suitable cathodic catalyst for direct methanol fuel cells.     

Covalent hybrid of hemin and mesoporous carbon as a high performance electrocatalyst for oxygen reduction

A high performance hemin and mesoporous carbon hybrid electrocatalyst for the oxygen reduction reaction (ORR) is developed by using hemin as the Fe–N-containing precursor to control the chemistry of the metal and the chemical composition of the carbon surface. As a first step, Hemin is used as the Fe–N-containing precursor to prepare the Fe–N-doped mesoporous carbon (H-MC) via a nano-casting process by using sucrose as a carbon source and mesoporous silica as a hard template. Hemin is then used as the Fe–N₄-containing precursor to prepare H-MC supported hybrid catalyst. The Fe-doped and N-doped mesoporous carbons are also prepared and the catalytic properties of the prepared catalysts for ORR in alkaline media are investigated. The results show that as compared with the much more expensive Pt/C catalyst, the hybrid catalyst obtained in this work exhibits not only a higher onset potential, but also a higher current density.     

Non-noble metal oxygen reduction electrocatalysts based on carbon nanotubes with controlled nitrogen contents

Nitrogen-doped carbon nanotubes (CN_x) were prepared via a floating catalyst chemical vapor deposition method using precursors consisting of ferrocene and melamine to control the nitrogen content. Structure, morphology and composition of all CN_x catalysts were characterized by SEM, TEM, and XPS. These results indicated that the surface nitrogen content (up to 7.7 at.%) increases with the increase of melamine used. Electrochemical methods were used to study the correlation between surface structure and the activity of oxygen reduction reaction (ORR) in acid and alkaline solutions. Electrochemical data indicated that the higher the nitrogen content is, the higher the oxygen reduction activity. Especially, the results from the rotating ring disk electrode technique demonstrated that CN_x (7.7%) has similar ORR activity and selectivity with commercial Pt/C in alkaline solution.     

Effect of carbon precursor and initial pH on cobalt-doped carbon xerogel for oxygen reduction

In this study, cobalt-doped carbon xerogel (Co-CX) was synthesised via sol-gel polymerisation of phenolic compounds (i.e., resorcinol, phenol and m-cresol) and formaldehyde, and this polymerisation was catalysed by cobalt nitrate and followed by a carbonisation process. The effect of the initial pH value (5.5, 6.5 and 7.5) as well as the type of carbon precursors on the structural properties of Co-CX was investigated via field emission scanning electron microscope (FESEM), Brunauer-Emmett-Teller (BET) and X-ray diffractometry (XRD). The catalytic activity of Co-CX for the oxygen reduction reaction (ORR) in 0.1 M KOH was studied using a rotating ring-disk electrode (RRDE) technique. The structural properties and ORR activities were affected by different initial pH values as well as the type of carbon precursor. A carbon precursor consisting of resorcinol-formaldehyde with an initial pH value of 7.5 exhibited the best catalytic activity. The initial pH plays an important role in promoting micro/mesopores. The FESEM and BET results revealed that Co doping promotes the formation of additional pores. The RRDE result indicated that Co-CX exhibited good catalytic activity that tends to favour a four-electron pathway.     

Boron doping induced electronic reconfiguration of Fe-Nx sites in N-doped carbon matrix for efficient oxygen reduction reaction in both alkaline and acidic media

Developing non-precious metal-based catalysts as the substitution of precious catalysts (Pt/C) in oxygen reduction reaction (ORR) is crucial for energy devices. Herein, a template and organic solvent-free method was adopted to synthesize Fe, B, and N doped nanoflake-like carbon materials (Fe/B/N–C) by pyrolysis of monoclinic ZIF-8 coated with iron precursors and boric acid. Benefiting from introducing B into Fe–N–C, the regulated electron cloud density of Fe-N_x sites enhance the charge transfer and promotes the ORR process. The as-synthesized Fe/B/N–C electrocatalyst shows excellent ORR activity of a half-wave potential (0.90 V vs 0.87 V of Pt/C), together with superior long-term stability (95.5% current density retention after 27 h) in alkaline media and is even comparable to the commercial Pt/C catalyst (with a half-wave potential of 0.74 V vs 0.82 V of Pt/C) in an acidic electrolyte. A Zn-air battery assembled with Fe/B/N–C as ORR catalyst delivers a higher open-circuit potential (1.47 V), specific capacity (759.9 mA h g^?1_Zn at 10 mA cm^?2), peak power density (62 mW cm^?2), as well as excellent durability (5 mA cm^?2 for more than 160 h) compared to those with commercial Pt/C. This work provides an effective strategy to construct B doped Fe–N–C materials as nonprecious ORR catalyst. Theoretical calculations indicate that introduction of B could induce Fe-N_x species electronic configuration and is favorable for activation of OH1 intermediates to promote ORR process.     

Nitrogen-doped carbon xerogel as high active oxygen reduction catalyst for direct methanol alkaline fuel cell

A novel catalyst based on nitrogen-doped carbon xerogel for oxygen reduction reaction (ORR) was prepared via a sol–gel process, following by the subsequent pyrolysis under ammonia atmosphere. The catalytic activity in alkaline media was optimized by tuning the metal (cobalt) ratio to the gel precursor. Sample with the optimum activity was characterized by transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) analysis and electrochemical measurements. Results show that the catalyst possesses an amorphous microstructure with nitrogen doped on the surface. The nitrogen-doped carbon xerogel displays comparable ORR activity and superior methanol tolerance than Pt/C in alkaline medium, demonstrating its promising application in direct methanol alkaline fuel cells as non-precious cathode catalyst.     

Direct immobilization of Pt-Ru alloy nanoparticles on nitrogen-doped carbon nanotubes with superior electrocatalytic performance

Taking the advantage of the inherent chemical activity arisen from the nitrogen incorporation for nitrogen-doped carbon nanotubes (NCNTs), we have developed a facile strategy for the construction of binary Pt-Ru/NCNT electrocatalysts. Alloyed Pt-Ru nanoparticles have been directly immobilized onto the outer surface of NCNTs without pre-modification due to the nitrogen participation. The Pt-Ru nanoparticles have a high dispersion, a narrow size distribution of 2.5-3.5 nm and tunable chemical composition. These catalysts have been evaluated for methanol oxidation and show good stability and better CO tolerance than the monometallic Pt/NCNT catalyst due to the bifunctional and electronic effects. The Pt₅Ru₅/NCNT catalyst shows superior electrocatalytic performance to the commercial Pt₅Ru₅/C catalyst. The easy fabrication and excellent performance of the NCNT-based Pt-Ru alloy catalysts indicate their potential application in direct methanol fuel cells.     

Synthesis of boron and nitrogen co-doped carbon nanotubes and their application in hydrogen storage

Boron and nitrogen codoped carbon nanotubes (B,N-CNTs) were synthesized by floating catalyst chemical vapor deposition (FCCVD) using ethanol, ferrocene, boric acid and imidazole as carbon source, catalyst, boron and nitrogen precursors, respectively. The samples were analyzed using transmission electron microscopy, Raman spectroscopy, thermogravimetric analysis and X-ray photoemission spectroscopy. 1.5 at% B and 1.34 at% N could be doped in the resultant structure, which has higher length (few μm) with higher thermal stability (621 °C). At pressure 16 bar, hydrogen adsorption for B,N-CNTs was found to be 1.96 and 0.35 wt% at 77 K and 303 K, respectively. Hydrogen storage as function of time was also reported for both the cases. The adsorption process follow pseudo second order kinetics. The present study reveals that the codoping of CNTs aid in tuning properties of CNTs for hydrogen storage application.