Cr2O3 nanoparticles boosting Cr–N–C for highly efficient electrocatalysis in acidic oxygen reduction reaction

Transition metal–nitrogen–carbon (M–N–C) catalysts have attracted significant attention for catalyzing oxygen reduction reactions (ORR). In this study, a porous Cr₂O₃@Cr–N–C catalyst with a small amount of Cr₂O₃ nanoparticles loaded on the surface of Cr–N₄–C nanomaterials was prepared using synergistic heat treatment (SHT) method with zeolite imidazole frameworks (ZIFs) as precursors. TEM and spherical aberration-corrected TEM results demonstrated the presence of hollow morphologies, Cr₂O₃ nanoparticles and atomic-level Cr distribution in Cr₂O₃@Cr–N–C. XPS, XRD and XAFS analysis indicated the coexistence of Cr₂O₃ nanoparticles and Cr–N₄ sites which were believed to act as active centers for ORR. In 0.1 M HClO₄, this material showed outstanding ORR catalytic activity with a half-wave potential of 0.78 V that was 40 mV higher than the traditional heat treatment derived Cr–N–C. It also revealed relatively low Tafel slope of 52.2 mV dec^?1; 4-electron pathway; remarkable stability and long-term durability. The improved ORR performance is mainly attributed to the synergy between Cr–N₄ active center and Cr₂O₃ nanoparticle. The SHT strategy reported here provides a new route to prepare highly efficient non-precious metal M?N–C catalysts with greater ORR activity and stability in acidic environments.     

Sponge tofu-like graphene-carbon hybrid supporting Pt–Co nanocrystals for efficient oxygen reduction reaction and Zn-Air battery

Developing highly efficient electro-catalysts for oxygen reduction reaction (ORR) by an economic and green manner is vital for the practical application of fuel cells and metal-air batteries. Herein, inspired by the manufacturing process of sponge tofu (Chinese Food), we develop a sponge tofu-like graphene-carbon hybrid supporting Pt–Co nanoparticles catalyst (denoted as Pt–Co/CB + RGO-3D) by a cheap and environment-friendly freeze-drying technology using ice as the template. The electrochemical tests show that Pt–Co/CB + RGO-3D exhibits approximately 16-fold higher ORR activity and better stability compared with Pt/C. Its excellent performance could be attributed to the high mass transfer efficiency and enhanced electron transfer capacity, which roots in its unique structure. Furthermore, the Pt–Co/CB + RGO-3D-based Zn-air battery exhibits superior performance, corroborating its commercial application potential. This work not only provides a prospective method to fabricate catalysts with porous structure but also offers an effective strategy to design highly efficient electrocatalysts with special structure.     

Mechanically activated Pt–Ni and Pt–Co alloys as electrocatalysts in the oxygen reduction reaction

Mixtures of powders of platinum with nickel or cobalt to obtain Ni_0.75Pt_0.25 or Co_0.75Pt_0.25 were mechanical alloyed by high energy ball milling. The results of crystal structure, morphology and electrocatalytic performance are presented for mechanically activated powders after 3 and 9 h of ball milling. Total solid solutions of Ni and Co with platinum were analyzed by X-ray diffraction after 3 h of ball milling. After 9 h of ball milling, in both cases, the total solid solution was accompanied by the appearance of NiO or CoO and ZrO associated with a redox reaction with the milling media. The presence of zirconium monoxide was confirmed by energy dispersive spectroscopy analysis. In both cases, an amorphization was detected. X ray absorption spectroscopy measurements showed changes in atomic and electronic environment of platinum, a reduction of the distance to the first coordination sphere and increased d-band vacancy vs pure Pt and Pt nanoparticles were observed for both studied systems. The electrocatalytic activity was determined using cyclic and linear voltammetry. The Co_0.75Pt_0.25 alloy milled for 9 h showed a higher electrochemical activity for the oxygen reduction reaction (ORR) compared with the other samples, including Pt-Etek. The degree of the ORR electrochemical activity was correlated with the presence of ZrO, which could affect the oxygen adsorption and improve the catalytic activity for the oxygen reduction reaction.     

ZrO2 anchored core-shell Pt–Co alloy particles through direct pyrolysis of mixed Pt–Co–Zr salts for improving activity and durability in proton exchange membrane fuel cells

Highly active and durable Pt-based catalysts for oxygen reduction reaction (ORR) are very important and necessary for the proton exchange membrane fuel cells (PEMFCs). In this paper, we report the preparation and performance study of ORR catalysts composed of core-shell Pt–Co alloy nanoparticles (NPs) on multi-walled carbon nanotubes (MWCNTs) anchored with ZrO₂ NPs (denoted as Pt–Co–ZrO₂/MWCNTs). Thanks to the unique three-phase structure, the mass activity of Pt–Co–ZrO₂/MWCNTs for ORR at 0.9 V versus reversible hydrogen electrode (RHE) is1577 mA mg_Pt^?1, which is ～6.6-fold higher than that of the commercial Pt/C (238 mA mg_Pt^?1). After 50,000 cycles for durability test, the mass activity of Pt–Co–ZrO₂/MWCNTs for ORR remained 88% of its initial value. In stark contrast, that of Pt/C kept only about 56.3% of its initial value. More importantly, its catalytic performance was fully observed/verified in a H₂-air PEMFC single cell test. When the Pt loading of Pt–Co–ZrO₂/MWCNTs loaded cathode was one fourth of that with commercial Pt/C as the cathode catalyst, comparable cell performance was achieved. More impressively, the MEA with Pt–Co–ZrO₂/MWCNTs underwent only 24.5% degradation in maximum power density after 30,000 accelerated durability tests (ADTs). However, the MEA with Pt/C after 30,000 ADTs exhibited 39.6% performance loss in maximum power density. The enhanced mass activity and catalytic durability of Pt–Co–ZrO₂/MWCNTs could be attributed to the core-shell Pt–Co alloy NPs with Pt-rich surface and the interface effect between Pt–Co alloy NPs and oxygen vacancy-rich ZrO₂ NPs. In addition, this research also provided a solution to the durability issue of cathodes without sacrificing ORR mass activity, which would promote practical application of PEMFCs.     

A highly efficient carbon-supported Pt electrocatalyst prepared by γ-irradiation for cathodic oxygen reduction

A simple, efficient and scalable approach is developed for synthesis of Vulcan XC-72(carbon)-supported Pt nanoparticles (NPs) that combines homogeneous deposition (HD) of Pt complex species through reaction with OH^- ions generated by in situ hydrolysis of urea and subsequent reduction by reducing species generated from radiolysis of water by γ-rays. This method not only avoids addition of any commonly used reducing agent, but also offers more uniform homogeneous dispersion of Pt NPs with much smaller particle size. Thus, when used as a cathode catalyst for proton exchange membrane fuel cell, the synthesized carbon-supported Pt NPs demonstrate excellent oxygen reduction electro–catalytic activity, higher Pt utilization efficiency, and considerably improved fuel cell polarization performance compared to those of Pt catalysts prepared with other synthesis strategies such as conventional NaBH₄ reduction and HD-ethylene glycol method as well as commercial Pt catalyst. The combined HD-γ-irradiation strategy is found to be simple, reproducible and efficient with mild synthesis condition and in particular, holds great promises for large scale production of highly efficient Pt-based catalysts for fuel cells.     

Ultrathin Co3O4–Pt core-shell nanoparticles coupled with three-dimensional graphene for oxygen reduction reaction

Design and synthesis of platinum catalysts within atomic level are of great significance for the practical application of fuel cells. We found that the ultrathin Co(OH)₂ nanoparticles can be converted into Co₃O₄–Co core-shell nanostructures through a thermal annealing process in reducing atmosphere, which are uniformly distributed on the surface of 3D graphene (3DG). The Co₃O₄–Co core-shell nanoparticles have been successfully transformed into Co₃O₄–Pt core-shell nanoparticles via a controlled replacement reaction. The Co₃O₄–Pt @3DG contains only a few atomic layers of Pt shell, and presents a high Pt utilization nanostructure. Besides, the 3D graphene serves as a catalysts carrier with open structure, and offers a three-dimensional molecular accessibility and conducive to mass transfer. Significantly, the optimized mass activity and specific activity of 1.018 A/mg_Pt and 2.17 mA/cm² have been achieved on Co₃O₄–Pt @3DG at 0.9 V vs RHE, which are 7.6- and 8.1- times higher than those of Pt/C (0.134 A/mg_Pt and 0.266 mA/cm²), respectively. The high activity is mainly attributed to the ultrathin core-shell structure with an ultrahigh Pt utilization, and the interaction between the near-surface Co₃O₄ and the surface Pt shell with a tensile strain to surface Pt shell, and the electrons transfer from Co to Pt.     

Pt and Pt–Ag nanoparticles supported on carbon nanotubes (CNT) for oxygen reduction reaction in alkaline medium

In this work, we investigated the effect of the carbon nanotubes (CNT) as alternative support of cathodes for oxygen reduction reaction (ORR) in alkaline medium. The Pt and Pt–Ag nanomaterials supported on CNT were synthesized by sonochemical method. The crystalline structure, morphology, particle size, dispersion, specific surface area, and composition were investigated by XRD, SEM-EDS, TEM, HR-TEM, N₂ adsorption-desorption and XPS characterization. The electrochemical activity for ORR was evaluated by cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) in alkaline medium. The electrochemical stability was researched by an accelerated degradation test (ADT). Pt/CNT showed the better electrocatalytic activity towards ORR compared with Pt–Ag/CNT and Pt/C. Pt/CNT exhibited higher specific activity (1.12 mA cm^?2 _Pt) than Pt/C (0.25 mA cm^?2 _Pt) which can be attributed to smaller particle size, Pt-CNT interaction, and Pt load (5 wt%). The Pt monometallic samples supported on CNT and Vulcan showed higher electrochemical stability after ADT than Pt–Ag bimetallic. The ORR activity of all materials synthesized proceeded through a four-electron pathway. Furthermore, the EIS results showed that Pt/CNT exhibited the lower resistance to the transfer electron compared with conventional Pt/C and Pt–Ag/CNT.     

Pulse-reverse electrodeposition of Pt–Co bimetallic catalysts for oxygen reduction reaction in acidic medium

Pt–Co electrodeposited by pulse reverse current on carbon cloth (CC) and glassy carbon (GC) are studied. On both substrates, applying a higher reverse current or a longer reverse-time increases the Pt content due to higher Co dissolution from Pt–Co structures, but does not affect the morphology. Despite similar morphologies and compositions deposited on CC or GC, the electrochemical behaviors of Pt–Co on both substrates are significantly different. Distinct hydrogen under-potential deposition (HUPD) adsorption/desorption peaks are not observed on CC, while well-defined peaks are established on GC. Oxygen reduction reaction (ORR) of Pt–Co on CC is significantly higher than on GC due to its highly porous structure. The ORR on GC changes with the Pt content controlled by varying the reverse pulse during electrodeposition, where Pt–Co with 58 at.% Pt or higher provides a better activity than Pt, with 77 at.% Pt having the highest ORR activity.     

Highly efficient PtCo nanoparticles on Co–N–C nanorods with hierarchical pore structure for oxygen reduction reaction

Developing platinum-based nanoparticles on carbon catalysts with high activity and stability for oxygen reduction reaction (ORR) is of great significance for the practical application of fuel cells. Herein, a synchronous strategy of preparing nano-sized PtCo supported on atomic Co and N co-doped carbon nanorods (PtCo/Co–N–C NR) was developed to replace the conventional method of impregnating Pt sources into ready-made carbon materials, in which metal-organic frameworks (MOFs) with Co and Zn ions of rhombic dodecahedron were first prepared using 2-methylimidazole as building block and then their morphology was transformed into porous nanorods via the reduction of Co ions to Co–B–O complex in the MOFs by NaBH₄; subsequently, Pt was deposited on the Co–Zn MOF nanorods through the displacement reaction of PtCl₆^2- and metallic Co and coordination between MOF and PtCl₆^2-; after pyrolysis and acid-leaching process, highly dispersed PtCo/Co–N–C NR was obtained. Attributed to its unique characteristics of hierarchical pore structure, uniform PtCo alloy nanoparticles with the average size of 7.0 nm and strong supporting interaction effect, the catalyst exhibits high ORR activity and stability with the mass activity of 577.0 mA mg^?1_Pt and specific activity of 1.4 mA cm^?2 at 0.9 V vs RHE in 0.1 M HClO₄, which is about 3.6 times and 3.5 times high than that of commercial Pt/C catalyst respectively. This strategy would provide a flexible route to develop highly active and stable ORR electrocatalysts with various morphologies for optimizing the exposure of active sites.     

Exploration of unalloyed bimetallic Au–Pt/C nanoparticles for oxygen reduction reaction

The synthesis of carbon-supported unalloyed Au–Pt bimetallic nanoparticles using polyol method at a temperature as low as 85 °C is reported. Various compositions of Au–Pt/C bimetallic nanoparticles are characterized using transmission electron microscopy (TEM), X-ray florescence (XRF), X-ray diffraction and cyclic voltammetry. Electron microscopy shows that the particles have a near-narrow size distribution that peaks at an average size of ∼5 to 6 nm. The electrocatalytic activity of Au–Pt/C nanoparticles towards the oxygen reduction reaction (ORR) is studied by linear sweep polarization measurements obtained using a rotating disc electrode (RDE). The results reveal that a four-electron transfer pathway is mainly operative for ORR and the half-wave potential for ORR on bimetallic Au–Pt/C (20%:20%) is ∼100 mV less negative when compared with that of Pt/C (home-made and E-Tek). Studies of the methanol oxidation reaction (MOR) on these catalysts show that the MOR activity is significantly lowered with increasing content of Au in Au–Pt/C.     

Morphological influence of graphitic carbon nanofibers by N–F dual-doping on Pt electrocatalytic activity and stability for oxygen reduction reaction in polymer electrolyte membrane fuel cells

Morphology of carbon nanofibers significantly effects Pt nanoparticles dispersion and specific interaction with the support, which is an important aspect in the fuel cell performance of the electrocatalysts. This study emphasizes, the defects creation and structural evolution comprised due to N–F co-doping on graphitic carbon nanofibers (GNFs) of different morphologies, viz. GNF-linearly aligned platelets (L), antlers (A), herringbone (H), and their specific interaction with Pt nanoparticle in enhancing the oxygen reduction reaction (ORR). GNFs–NF–Pt catalysts exhibit better ORR electrocatalytic activity, superior durability that is solely ascribed to the morphological evolution and the doped N–F heteroatoms, prompting the charge density variations in the resultant carbon fiber matrices. Amongst, H–NF–Pt catalyst performed outstanding ORR activity with exceptional electrochemical stability, which shows only 20 mV loss in the half-wave potential whilst 100 mV loss for Pt/C catalyst on 20,000 potential cycling. The PEMFC comprising H–NF–Pt as cathode catalyst with minimum loading of 0.10 mg cm^?2, delivers power density of 0.942 W cm^?2 at current density of 2.50 A cm^?2 without backpressures in H₂–O₂ feeds. The H–NF–Pt catalyst owing to its hierarchical architectures, performs well in PEMFC at the minimized catalyst loading with outstanding stability that can significantly decrease total price for the fuel cell.     

Electrocatalytic activity of Pt–Pd electrocatalysts for the oxygen reduction reaction in proton exchange membrane fuel cells: Effect of supports

Pt–Pd electrocatalysts supported on different types of support including domestic Hicon Black (HB), multi-walled carbon nanotubes (MWCNT) and titania (TiO₂) were prepared by a combined approach of impregnation and seeding, and compared to that prepared using the commercial Vulcan XC-72 (C). Their oxygen reduction reaction (ORR) activities in an acid electrolyte (0.5 M H₂SO₄) and in a single proton exchange membrane (PEM) fuel cell were evaluated. The type of support was found to affect the Pt–Pd electrocatalyst morphology and ORR activity. The Pt–Pd/C electrocatalyst had the smallest Pt particle size, better catalyst dispersion and a higher Pt:Pd M ratio compared to that of other types of supported Pt–Pd electrocatalysts. However, both in the acid solution and in a single PEM fuel cell, the ORR activities of the Pt–Pd/HB and Pt–Pd/CNT electrocatalysts were comparable to that of the Pt–Pd/C one. The ORR pathway of all supported Pt–Pd electrocatalysts were close to the four-electron pathway.     

Electrochemical activity and stability of dealloyed Pt–Cu and Pt–Cu–Co electrocatalysts for the oxygen reduction reaction (ORR)

A comparative study of the electrochemical stability of Pt₂₅Cu₇₅ and Pt₂₀Cu₂₀Co₆₀ alloy nanoparticle electrocatalysts in liquid electrolyte half-cell environment was conducted. The aforementioned catalysts were shown to possess improved resistance to electrochemical surface area (ECSA) loss during voltage cycling relative to commercially available pure Pt electrocatalysts. The difference in ECSA loss was attributed to their initial mean particle size, which varied depending on the temperature at which the alloy catalysts were prepared (e.g. 600, 800 and 950 °C). Higher preparation temperatures resulted in larger particles and lead to lower ECSA loss. Liquid electrolyte environment short-term durability testing (5000 voltages cycles) revealed the addition of cobalt to be beneficial as ternary compositions exhibited stability advantages over binary catalysts.     

Fe–N–Si tri-doped carbon nanofibers for efficient oxygen reduction reaction in alkaline and acidic media

The most ideal substitute for Pt/C to catalyze the oxygen reduction reaction (ORR) is the transition metal and nitrogen co-doped carbon-based material (TM-N-C). However, large particles with low catalytic activity are formed easily for the transition metals during high-temperature carbonization. Herein, PAN nanofibers uniformly distributed with FeCl₃ were coated with SiO₂ and then carbonized to obtain Fe–N–Si tri-doped carbon nanofibers catalyst (Fe–N–Si-CNFs). The SiO₂ can further anchor the Fe atoms, thus preventing agglomeration during the carbonization process. Meanwhile, Si atoms have been doped in CNFs during this process, which is conducive to the further improvement of catalytic performance. The Fe–N–Si-CNFs catalyst has a 3D network structure and a large specific surface area (809.3 m² g⁻¹), which contributes to catalyzing the ORR. In alkaline media, Fe–N–Si-CNFs exhibits superior catalytic performance (E_1/2 = 0.86 V vs. RHE) and higher stability (9.6% activity attenuation after 20000s) than Pt/C catalyst (20 wt%).     

Pd decorated Co–Ni nanowires as a highly efficient catalyst for direct ethanol fuel cells

The storage and conversion of energy necessitates the use of appropriate electrochemical systems and chemical reaction catalysts. This work presents newly developed catalysts for electrooxidation of ethanol in an alkaline medium. Nanocatalysts composed of Co–Ni nanowires (Co–Ni NWs) decorated with Pd nanoparticles (Pd NPs) were made at varying metal ratios and their chemical composition and structure was investigated in detail. The synthesis involved a wet chemical reduction assisted by a magnetic field, which led to the generation of NWs, followed by the deposition of spherical Pd NPs on their surface. The best catalytic activity was obtained for the catalyst made of Co₃–Ni₇ decorated with Pd NPs, which exhibited EOR of 8003 mA/mg_Pd for only 0.86 wt% of Pd loading. The results can be explained by the synergistic effect between the morphology of the bimetallic support and the favorable interaction of oxophilic Co, Ni with catalytic Pd.     

Effect of pretreatment on Pt–Co/C cathode catalysts for the oxygen reduction reaction

Carbon supported Pt and Pt–Co electrocatalysts for the oxygen reduction reaction in low temperature fuel cells were prepared by the reduction of the metal salts with sodium borohydride and sodium formate. The effect of surface treatment with nitric acid on the carbon surface and Co on the surface of carbon prior to the deposition of Pt was studied. The catalysts where Pt was deposited on treated carbon the ORR reaction preceded more through the two electron pathway and favored peroxide production, while the fresh carbon catalysts proceeded more through the four electron pathway to complete the oxygen reduction reaction. NaCOOH reduced Pt/C catalysts showed higher activity that NaBH₄ reduced Pt/C catalysts. It was determined that the Co addition has a higher impact on catalyst activity and active surface area when used with NaBH₄ as reducing agent as compared to NaCOOH.     

Carbon supported nano-sized Pt–Pd and Pt–Co electrocatalysts for proton exchange membrane fuel cells

Nano-sized Pt–Pd/C and Pt–Co/C electrocatalysts have been synthesized and characterized by an alcohol-reduction process using ethylene glycol as the solvent and Vulcan XC-72R as the supporting material. While the Pt–Pd/C electrodes were compared with Pt/C (20 wt.% E-TEK) in terms of electrocatalytic activity towards oxidation of H₂, CO and H₂–CO mixtures, the Pt–Co/C electrodes were evaluated towards oxygen reduction reaction (ORR) and compared with Pt/C (20 wt.% E-TEK) and Pt–Co/C (20 wt.% E-TEK) and Pt/C (46 wt.% TKK) in a single cell. In addition, the Pt–Pd/C and Pt–Co/C electrocatalyst samples were characterized by XRD, XPS, TEM and electroanalytical methods. The TEM images of the carbon supported platinum alloy electrocatalysts show homogenous catalyst distribution with a particle size of about 3–4 nm. It was found that while the Pt–Pd/C electrocatalyst has superior CO tolerance compared to commercial catalyst, Pt–Co/C synthesized by polyol method has shown better activity and stability up to 60 °C compared to commercial catalysts. Single cell tests using the alloy catalysts coated on Nafion-212 membranes with H₂ and O₂ gases showed that the fuel cell performance in the activation and the ohmic regions are almost similar comparing conventional electrodes to Pt–Pd anode electrodes. However, conventional electrodes give a better performance in the ohmic region comparing to Pt–Co cathode. It is worth mentioning that these catalysts are less expensive compared to the commercial catalysts if only the platinum contents were considered.     

Shape-tunable Pt–Ag nanocatalysts with excellent performance for oxygen reduction reaction

Shape-tunable PtAg nanocatalysts including PtAg nanoflowers (NFs) and PtAg nanowires (NWs) are prepared by a facile hydrothermal reduction method, via adjusting the precursor ratio of Pt/Ag and subsequent UV-irradiation. Physicochemical characterizations reveal that the as-prepared catalysts have a porous structure, which forms from the conversion of AgCl to Ag nanoparticles. These features favor both oxygen mass transfer and accessibility of active sites. The as-prepared Pt₁Ag₄ NWs exhibit superior catalytic performances for ORR. The mass activity of Pt₁Ag₄ NWs is 11.4 times higher than that of 20% Pt/C. More important, the electrochemically active surface area (ECSA) of Pt₁Ag₄ NWs is 2.5 times larger than that of commercial Pt/C.     

Cu-MOF@Co-MOF derived Co–Cu alloy nanoparticles and N atoms co-doped carbon matrix as efficient catalyst for enhanced oxygen reduction

We prepare a series of N-containing Cu-MOF@Co-MOF core-shell templates by employing two-step feed-in pathway and then step by step calcining these materials to obtain the N-doped carbon layers encapsulated Co–Cu alloy nanoparticles as efficient catalysts for enhanced oxygen reduction. The purpose of Cu-MOF designed as core materials is to increase the number of openly active sites when the templates are calcined at high temperature. During calcining, the Cu atoms facilitate the dispersion of Co on the surface of Co–Cu alloy nanoparticles, which efficiently avoid the agglomeration of Co during carbonization. When being used as cathode oxygen reduction catalysts, the optimal Co–Cu(3:1)@CN-900 material exhibits outstanding performance that can be comparable with the 20 wt% Pt/C catalysts, and the onset potential and half-wave potential of Co–Cu(3:1)@CN-900 is 60 mV and 37 mV higher than that of monometallic Co@CN-900 catalysts, respectively. Moreover, the active sites of Co–Cu(3:1)@CN-900 catalysts are also carefully investigated.     

Efficient electrocatalyst of Pt–Fe/CNFs for oxygen reduction reaction in alkaline media

Transition metal iron-based catalysts are promising electrocatalysts for oxygen reduction reaction (ORR), and they have the potential to replace noble metal catalysts. The one-dimensional of carbon nanofibers with tubular structure can effectively promote the electrocatalytic activity, which facilitates electron transport. Herein, the Pt–Fe/CNFs were synthesized by electrospinning and subsequent calcination. Benefiting from the advantages of one-dimensional structure, Pt–Fe/CNFs-900 with fast electrochemical kinetics and excellent stability for ORR with excellent onset of 0.99 V, a low Tafel slope of 62 mV dec⁻¹ and high limiting current density of 6.00 mA cm⁻². Long-term ORR testing indicated that the durability of this catalyst was superior to that of commercial Pt/C in alkaline electrolyte. According to RRDE test, the ORR reaction process of Pt–Fe/CNFs-900 was close to four-electron transfer routes.