H2-induced thermal treatment significantly influences the development of a high performance low-platinum core-shell PtNi/C alloyed oxygen reduction catalyst

In the purpose of maximizing the utilization of noble metal Pt in oxygen reduction catalysts, we illustrate a synthesis method of preparing the low-platinum PtNi/C alloyed oxygen reduction reaction (ORR) catalyst, which is developed through the H₂-induced treatment to a glucose reduced PtNi/C alloy. After post-treatment with H₂/N₂ mixture gases, this catalyst displays excellent ORR catalytic activity and durability for the synergetic influences of electronic and geometry effects on catalysts during the alloying. Specifically, the as-prepared PtNi/C (350°C-6 h) sample delivers preponderant ORR activity with only 53.5% Pt usage than the commercial Pt/C. The specific activity and mass activity are corresponding 7.49 times and 3.5 times to the commercial Pt/C. This catalyst exhibits excellent ORR catalytic activity after 10 000 potential cycles in acid, which benefits from the well alloyed core-shell structure of PtNi/C. H₂-induced thermal treatment has significant effects on the development of high performance low-platinum PtNi/C alloy catalyst, and plays the significant role in the formation of well-alloyed core-shell structures. The lowered d-band center is believed to facilitate ORR catalysis through weakening the adsorption of intermediate oxygen species on the alloyed Pt surface. Therefore, PtNi/C(350°C-6 h) alloyed catalyst possesses outstanding ORR catalytic activity with much lower Pt loading.     

Enhanced bioelectricity generation and cathodic oxygen reduction of air breathing microbial fuel cells based on MoS2 decorated carbon nanotube

Increasing efforts have been devoted to enhancing the cathode activity towards oxygen reduction and improve power generation of air breathing microbial fuel cells. Exploring non-precious metal and highly active cathodic catalyst plays a key role in improving cathode performance. Our work aims to investigate the electrocatalyst behavior and power output of the single-chamber MFC equipped with carbon nanotubes hybridized molybdenum disulfide nanocomposites (CNT/MoS₂) cathode. MoS₂ nanosheets embedded into the CNTs network structure is synthesized by a facile hydrothermal method. The CNT/MoS₂-MFC achieves a maximum power density of 53.0 mW m⁻², which is much higher than those MFCs with pure CNTs (21.4 mW m⁻²) or solely MoS₂ (14.4 mW m⁻²) cathode. The oxygen reduction reaction (ORR) test also demonstrates a promoted electrocatalytic activity of synthesized material, which may be attributed to the special interlaced structure and abundant oxygen chemisorption sites of CNT/MoS₂. Such CNTs-based noble-metal-free catalyst presents a new approach to the application of MFCs cathode materials.     

Carbon-supported Pd nanocatalyst modified by non-metal phosphorus for the oxygen reduction reaction

A carbon-supported palladium catalyst modified by non-metal phosphorus (PdP/C) has been developed as an oxygen reduction catalyst for direct methanol fuel cells. The PdP/C catalyst was prepared by the sodium hypophosphite reduction method. The as-prepared Pd nanoparticles have a narrow size distribution with an average diameter of 2 nm. Energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) results indicate that P enters into the crystal lattice of Pd and forms an alloy. The PdP/C catalyst has an oxygen reduction reaction (ORR) activity comparable to the commercial Pt/C catalyst and a higher activity than the Pd/C catalyst synthesized by the conventional NaBH₄ reduction method. Its high catalytic activity can be attributed to its small size, lower relative crystallinity, and the formation of PdP alloy.     

Natural aloe vera derived Pt supported N-doped porous carbon: A highly durable cathode catalyst of PEM fuel cell

Evolution of highly durable electrocatalyst for oxygen reduction reaction (ORR) is the most critical barrier in commercializing polymer electrolyte membrane fuel cell (PEMFC). In this work, Pt deposited N-doped mesoporous carbon derived from Aloe Vera is developed as an efficient and robust electro catalyst for ORR. Due to its high mesoporous nature, the aloe vera derived carbon (AVC) play a very vital role in supporting Pt nanoparticles (NPs) with N-doping. After doping N into AVC, more defects are created which facilitates uniform distribution of Pt NPs leading to more active sites towards ORR. Pt/N-AVC shows excellent ORR activity when compared with commercial Pt/C and showing a half wave potential (E_1/2–0.87 V Vs. RHE) and reduction potential (E_red ~ 0.72 V Vs. RHE) towards ORR. Even after 30,000 potential cycles, Pt/N-AVC shows in its E_1/2 only ~5 mV negative shift and lesser agglomeration of Pt NPs is seen in the catalyst. In membrane electrode assembly (MEA) fabrication, Pt/N-AVC as a cathode catalyst in a PEMFC fixture and performance were studied. The Pt/N-AVC shows good performance, which proves the potential application of this naturally available bio derived carbon, which serves as an excellent high durable support material in PEMFC. All these features show that the Pt/N-AVC is the most stable, efficient and suitable candidate for ORR catalyst.     

PtCo incorporated porous carbon nanofiber as a promising oxygen reduction electrocatalyst

Designing oxygen reduction reaction (ORR) catalysts with high activity and long durability is significant for the development of proton exchange membrane fuel cells. Herein, the optimized platinum nanowires are used as templates for inducing growth of cobalt-containing metal-organic framework, deriving uniform nanofibers. After the calcination, the metal ions are transferred into the nitrogen-rich porous carbon, and wrapped by the carbon skeleton to form the PtCo bimetal incorporated nanofibers as high-performance ORR electrocatalyst. The Pt₄Co@NC-900 catalyst yields high specific activity (1.37 mA cm⁻²) in comparison to Pt/C (0.38 mA cm⁻²). The mass activity (MA) of Pt₄Co@NC-900 catalyst is approximately 3.8-fold higher than that of the commercial Pt/C under acidic conditions. After the accelerated durability tests, the Pt₄Co@NC-900 catalyst presents only 16% loss in MA, while Pt/C catalyst retains 73.0% of the initial MA. The improved ORR performance can be ascribed to the synergistic interaction between Co and Pt.     

A highly stable TiB2-supported Pt catalyst for polymer electrolyte membrane fuel cells

Pt nanoparticles supported on TiB₂ conductive ceramics (Pt/TiB₂) have been prepared through a liquid reduction method, where the TiB₂ surfaces are stabilized with perfluorosulfonic acid. The prepared Pt/TiB₂ catalyst is characterized with X-ray diffraction (XRD) and TEM techniques, and a rotating disk electrode (RDE) apparatus. The Pt nanoparticles are found to uniformly disperse on the surface of the TiB₂ particles with narrow size distribution. The electrochemical stability of Pt/TiB₂ is evaluated and found highly electrochemically stable compared to a commercial Pt/C catalyst. Meanwhile, the catalyst also shows comparable performance for oxygen reduction reaction (ORR) to the Pt/C. The mechanism of the remarkable stability and comparable activity for ORR on Pt/TiB₂ is also proposed and discussed.     

High stability and activity of Pt electrocatalyst on atomic layer deposited metal oxide/nitrogen-doped graphene hybrid support

A novel nanostructured support of ZrO₂/nitrogen-doped graphene nanosheets (ZrO₂/NGNs) hybrid was synthesized successfully by atomic layer deposition (ALD) technology to significantly improve the activity and stability of Pt electrocatalyst. Electrochemical test shows that Pt–ZrO₂/NGNs catalyst has 2.1 times higher activity towards methanol oxidation reaction (MOR) than Pt/NGNs catalyst, due to the promotion by ZrO₂ to the MOR on Pt surface. Pt–ZrO₂/NGNs catalyst has higher electrochemical surface area (ECSA) and better oxygen reduction reaction (ORR) activity than Pt/NGNs catalyst. Pt–ZrO₂/NGNs catalyst has also demonstrated 2.2 times higher durability than that of Pt/NGNs. The enhanced activity and durability were attributed to the unique triple-interaction of ZrO₂–Pt–NGNs. These findings indicate that metal oxide-metal-support is a promising catalyst structure for low temperature fuel cells.     

Electrocatalysis of oxygen reduction when varying the mass ratio of metal nanoparticles to carbon support for catalysts with a 10 to 10 to 80 mol% of Pt and Pd on Ag

The reduction of total Pt-loading in a cathode catalyst without sacrificing performance is one of the key objectives for the large-scale commercialization of proton exchange membrane fuel cell (PEMFC) technology. A core-shell type nanostructured catalyst with a Pt-loading 20 times lower than a commercial catalyst is demonstrated herein to be more active for the electrocatalysis of the oxygen reduction reaction (ORR) in acid electrolyte. The weight ratio of metal nanoparticles on carbon support is the key to achieving the highest ORR activity in a series of silver-based catalysts, all with 10 mol percent of Pt and 10 mol percent of Pd over 80 mol percent of silver (Ag) and supported on untreated Vulcan carbon to form an electrocatalyst (Ag@Pt₁₀Pd₁₀/C) with either 5, 10, 20 or 30 wt% of total metals on carbon; which correspond to a Pt concentration around 1, 2, 3 and 5 wt%, respectively. All metal nanostructures on carbon show a similar morphology, size and structure. Thin films of these four Ag@Pt₁₀Pd₁₀/C catalysts on rotating disk electrodes (TF-RDEs) all shown a 4-electrons pathway for the ORR and give higher exchange current densities (j_o > 3.8 mA/cm²) than a commercial Etek Pt₂₀/C catalyst (j_o = 2.4 mA/cm²). The Ag@Pt₁₀Pd₁₀/C catalyst with 5 wt% of total metals (1 wt% of Pt) on carbon gives the best electrocatalysis; reducing molecular oxygen to water two times faster and generating 25% higher current per milligram of platinum (mass activity) than the commercial catalyst (Pt₂₀/C). Therefore, the Ag@Pt₁₀Pd₁₀/C catalyst with 5 wt% of total metals is a new catalyst for ORR for a PEMFC with a lower Pt loading and cost.     

Spinel-type NiCo2O4 with abundant oxygen vacancies as a high-performance catalyst for the oxygen reduction reaction

Spinel-type nickel cobaltite with numerous oxygen vacancies is successfully synthesized by hydrothermal and thermal reduction using hydrogen. The effects of oxygen vacancies on the electrochemical activity and stability for the oxygen reduction reaction are investigated. The prepared catalyst displays significantly enhanced oxygen reduction reaction (ORR) catalytic performance under alkaline conditions, which is comparable to that of commercial Pt/C. The oxygen-deficient NiCo₂O₄ exhibits a very high limiting current density of −5.44 mA cm⁻² with onset and half-wave potentials of 0.93 and 0.78 V versus the reversible hydrogen electrode (RHE), respectively. Additionally, it shows excellent durability and resistance to methanol. The enhanced ORR activity and stability of the catalyst can be ascribed to the synergistic effects of the relatively large electrochemical surface area, more exposed active sites, and good electrical conductivity derived from abundant oxygen vacancies.     

Preparation of iron and nitrogen co-doped carbon material Fe/N-CCM-T for oxygen reduction reaction

In this paper, iron and nitrogen co-doped carbon material with nanotube structure (Fe/N-C_CM-T) was synthesized by pyrolyzing a mixture of Fe salt, chitosan and melamine and displayed high electrocatalytic performance for oxygen reduction reaction (ORR). The structure of the Fe/N-C_CM-T was characterized and their ORR performance in alkaline media was investigated by linear sweep voltammetry, cyclic voltammetry and chronoamperometry. Fe/N-C_CM-T displayed better ORR performance than other carbon materials like Fe/N-C_C-800. The Fe/N-C_CM-800 with a large surface area (302.5 m²/g) especially exhibited the best ORR electrocatalytic performance among the prepared carbon materials, which was also proved by its similar Tafel slope (76 mV decade^?1) to Pt/C catalyst (74 mV decade^?1). Fe/N-C_CM-800 showed similar ORR activity as commercial Pt/C catalyst, but superior tolerance to methanol and stability. Such high ORR performance of the Fe/N-C_CM-T can be attributed to its nanotube structure, high specific surface area (SSA), high graphitic-N and pyridinic-N contents.     

Pd9Au1@Pt/C core-shell catalyst prepared via Pd9Au1-catalyzed coating for enhanced oxygen reduction

The scarcity and poor long-term stability of Pt has greatly hindered its commercial application as oxygen reduction reaction (ORR) catalyst. In this work, carbon-supported Pd₉Au₁ alloy particles with a Pd/Au molar ratio of 9:1 synthesized by using an ethylene glycol-based reduction method were used to catalyze ethanol oxidation to coat Pd₉Au₁ core with Pt atomic layers to synthesize Pd₉Au₁@Pt/C catalyst. Physical characterization shows that the as-synthesized Pd₉Au₁@Pt/C catalysts present a well-defined core-shell structure and the surface Pt layers can be well controlled by tuning the amount of Pt precursor added during synthesis. Electrochemical characterization shows that among the synthesized catalysts Pd₉Au₁@Pt₂/C with 2 atomic Pt layers exhibits the best activity and excellent stability for ORR, as evidenced by its even increased half-wave potential after 10000 potential cycles between 0.6 and 1 V in O₂-saturated 0.1 M HClO₄ solution. This enhanced ORR activity and stability of Pd₉Au₁@Pt₂/C catalyst can be attributed to the compressive strain and stabilizing effect of Pd₉Au₁ core on Pt shell.     

Co/NC-Gr composite derived from ZIF-67: Effects of preparation method on the structure and electrocatalytic performance for oxygen reduction reaction

Co/NC-Gr catalyst is prepared by in-situ growth of porous ZIF-67 on graphene (Gr) sheets followed by calcination. The effect of preparation method on the structure and catalytic performance of Co/NC-Gr for oxygen reduction reaction is studied. By optimizing the preparation process, the large Gr sheets are wrapped around the surfaces of the Co-incorporated polyhedral N-doped carbon skeleton. This structure plays a great role in connecting different Co/NC rhombic dodecahedron (RD), leading to high conductivity and fast mass transportation. The higher-content of pydinic-N and graphitic-N in Co/NC-Gr-A than those in Co/NC make it have enhanced catalytic activity. The porous Co/NC-Gr-A shows the highest ORR activity and stability through a dominant 4e⁻ process. The Co/NC-Gr-A exhibits much higher methanol-tolerant ability than Pt/C. The yield of H₂O₂ during ORR on Co/NC-Gr-A is very close to that on commercial Pt/C.     

Efficient oxygen reduction electrocatalysis on Mn3O4 nanoparticles decorated N-doped carbon with hierarchical porosity and abundant active sites

Transition metal on nitrogen-doped carbons (M-N-C, M = Fe, Co, Mn, etc.) are a group of promising sustainable electrocatalysts toward oxygen reduction reaction (ORR). Compared to its Fe, Co analogues, Mn–N–C possesses the advantage of being inert for catalyzing Fenton reaction, and thus is expected to offer higher durability, but its ORR activity needs essential improvement. Herein, an efficient Mn–N–C ORR catalyst composed of Mn₃O₄ nanoparticles supported on nitrogen-doped carbon was successfully synthesized by pyrolysis of cyanamide/Mn-incorporated polydopamine (PDA) film coated carbon black (CB), where the presence of N-rich cyanamide confers abundant Mn-N_x active sites and rich micropore/mesopores to the catalyst. In an alkaline medium, as-synthesized Mn–N–C electrocatalyst outperforms commercial Pt/C catalyst in terms of onset potential (0.98 V, vs. RHE), half-wave potential (0.868 V, vs. RHE), and limiting current density. Meanwhile, it exhibits excellent durability and resistance to methanol. In a Zinc-air primary battery, it demonstrates better performance as a cathodic catalyst than Pt/C.     

Ultrafine iron oxide nanoparticles supported on N-doped carbon black as an oxygen reduction reaction catalyst

An oxygen reduction reaction (ORR) catalyst comprising ultrafine iron oxide nanoparticles supported on N-doped Vulcan carbon (FeO_1.4/N-C) was prepared via a two-step method. X-ray photoelectron spectroscopy revealed the iron oxide nanoparticles comprised Fe₂O₃ and FeO phases with a combined average oxidation state of 2.8. The FeO_1.4/N-C catalyst produced an ORR onset potential of −0.056 V and a half-wave potential of −0.190 V in alkaline media, which was comparable to that of commercial Pt/C catalyst. Moreover, FeO_1.4/N-C had higher methanol tolerance than Pt/C catalyst and thus affords a promising non-precious metal ORR catalyst for fuel cells.     

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.     

Composition-tunable PtCu porous nanowires as highly active and durable catalyst for oxygen reduction reaction

To accelerate the commercialization of fuel cells, many efforts have been made to develope highly active and durable Pt-based catalyst for oxygen reduction reaction (ORR). Herein, PtCu porous nanowires (PNWs) with controllable composition are synthesized through an ultrasound-assisted galvanic replacement reaction. The porous structure, surface strain, and electronic property of PtCu PNWs are optimized by tuning composition, which can improve activity for ORR. Electrochemical tests reveal that the mass activity of Pt_0.5Cu_0.5 PNWs (Pt/Cu atomic ratio of 1:1) reaches 0.80 A mg_Pt^?1, which is about 5 times higher than that of the commercial Pt/C catalyst. Notably, the improved activity of the porous nanowire catalyst is also confirmed in the single-cell test. In addition, the large contact area with the carrier and internal interconnection structure of Pt_0.5Cu_0.5 PNWs enables them to exhibit much better durability than the commercial Pt/C catalyst and Pt_0.5Cu_0.5 nanotubes in accelerated durability test.     

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.     

Pt overgrowth on carbon supported PdFe seeds in the preparation of core-shell electrocatalysts for the oxygen reduction reaction

In this study, a novel core-shell structured Pd₃Fe@Pt/C electrocatalyst, which is based on Pt deposited onto carbon supported Pd₃Fe nanoparticles, is prepared for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). The carbon supported Pd₃Fe nanoparticles act as seeds to guide the growth of Pt. The formation of the core-shell structured Pd₃Fe@Pt/C is confirmed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and electrochemical characterization. The higher surface area of the synthesized catalyst suggests that the utilization of Pt in the Pd₃Fe@Pt/C catalyst is higher than that in Pt/C. Furthermore, better electrocatalytic performance than that of Pt/C and Pd₃Fe/C catalyst is observed in the ORR which follows a four-electron path. Consequently, the results indicate that the Pd₃Fe@Pt/C catalyst could be used as a more economically viable alternative for the ORR of PEMFCs.     

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.