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The H3PO4 poisoning problem severely limits the performance of high‐temperature proton exchange membrane fuel cells (HT‐PEMFCs) using the H3PO4‐doped polybenzimidazole as electrolyte membrane. Herein, the micropore‐rich carbon shell‐confined Pt‐based nanoparticles (Pt@MPC) with a Pt loading of 44.9 wt% is developed as the H3PO4 poisoning‐resistant electrocatalyst for oxygen reduction reaction (ORR), which possesses both high ORR activity and stability. The half‐wave potential (E1/2) of 0.898 V and electrochemical active surface area (ECSA) of 62.3 m2 gPt−1 are superior to commercial 40 wt% Pt/C (E1/2 = 0.892 V; ECSA = 53.1 m2 gPt−1). Pt@MPC remains almost unchanged after the accelerated durability test of 10 000 cycles. Moreover, Pt@MPC exhibits remarkable H3PO4 tolerance as its negative shift of E1/2 (82 mV) is less in H3PO4‐containing electrolyte compared with commercial Pt/C (114 mV). This can be attributed to the steric effect of the micropore‐rich carbon, which enables the selective transport of reactants while inhibiting H3PO4. The HT‐PEMFCs assembled with Pt@MPC (0.7 mgPt cm−2) exhibit a maximum power density of 674 mW cm−2 under the H2‐O2 condition and outperform the commercial Pt/C (616 mW cm−2). This strategy provides a new direction for the design of ORR catalysts toward HT‐PEMFCs with better phosphoric acid poisoning resistance. [ABSTRACT FROM AUTHOR]

Iron‐nitrogen‐doped carbon (Fe‐NC) is an ideal candidate to replace Pt‐based oxygen reduction reaction (ORR) electrocatalysts due to its low cost and comparably high intrinsic activity. To further enhance the ORR performance of Fe‐NC electrocatalysts, efforts have been focused on two main methods. One is to enhance the intrinsic activity of FeNx sites through electronic and geometric regulation, and the other is to increase the density of active sites by introducing high‐nitrogen‐containing precursors or co‐doping methods. Herein, we report a strategy to further increase the Fe loading through the introduction of a trace amount of Cu atoms. Significant enhancement of the electrocatalytic ORR property is observed in the as‐prepared Fe and Cu co‐doped electrocatalyst with superior half‐wave potential (E1/2) in both alkaline and acid electrolyte. Experimental and theoretical study reveals that the introduction of a trace amount of Cu atoms is beneficial for the formation of FeN4 sites, owing to the reduced formation energy. This work opens up a wide avenue to further increase the Fe loading in Fe‐NC electrocatalysts through bimetal co‐doping method. [ABSTRACT FROM AUTHOR]

The significant use of platinum for catalyzing the cathodic oxygen reduction reactions (ORRs) has hampered the widespread use of polymer electrolyte membrane fuel cells (PEMFCs). The construction of well-defined electrode architecture in nanoscale with enhanced utilization and catalytic performance of Pt might be a promising approach to address such barrier. Inspired by the highly efficient catalytic processes in enzymes with active centers embedded in charge transport pathways, here we demonstrate for the first time a design that allocates platinum nanoparticles (Pt NPs) at the boundaries with dual-functions of conducting both electrons by aid of polypyrrole and protons via Nafion® ionomer within hierarchical nanoarrays. By mimicking enzymes functionally, an impressive ORR activity and stability is achieved. Using this brand new electrode architecture as the cathode and the anode of a PEMFC, a high mass specific power density of 5.23 W mg−1Pt is achieved, with remarkable durability. These improvements are ascribed to not only the electron decoration and the anchoring effects from the Nafion® ionomer decorated PPy substrate to the supported Pt NPs, but also the fast charge and mass transport facilitated by the electron and proton pathways within the electrode architecture. [ABSTRACT FROM AUTHOR]

Phosphoric acid (PA), utilized as an electrolyte in high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs), has been observed to exert a detrimental effect on oxygen reduction reaction (ORR) electrocatalyst, consequently compromising cell performance. To comprehensively elucidate the impact of phosphoric acid on ORR, this study employs a range of electrochemical techniques, including electrochemical impedance spectroscopy and voltammetry method. The negative influence of PA on commercial Pt/C electrocatalyst manifests differently under various potentials and PA concentrations. Upon the introduction of PA, the decay rate and amplitude of ECSA, as calculated by H upd adatoms, are notably smaller compared to the kinetic current density generated by the oxygen reduction reaction. Particularly, in the kinetic-controlled potential range, the negative impact of PA becomes more pronounced at higher electrode potentials, accompanied by a significantly steeper Tafel slope. Additionally, the EIS results suggest that phosphoric acid may gradually transform into polyphosphoric acid at a high concentration, accentuating the poisoning effect of PA under steady-state conditions. However, a high PA concentration can substantially alter the electrolyte properties, potentially leading to an inaccurate assessment of PA tolerance in electrocatalysts. Hence, it is imperative to consider the appropriate PA concentration when evaluating PA tolerance and to discern the poisoning mechanism under different electrode potentials. [ABSTRACT FROM AUTHOR]

Researching of high performance and low-cost oxygen reduction reaction (ORR) electrocatalysts is one of the core issues for the rapid development of energy conversion and storage devices. Herein, a N and S dual-doped three-dimensional (3D) interconnected mesoporous carbon catalyst (CNS) was constructed via a facile hydrothermal-pyrolysis strategy. Benefiting from the 3D interconnected mesoporous architecture, CNS was endowed with a fast oxygen mass transfer rate together with plentiful of accessible active centers on the surface. Its ORR half-wave potential (E 1/2 ， 0.87 V) surpasses commercial Pt/C catalyst 50 mV in alkaline media. Its E 1/2 negatively shifts only 2 mV after 8000 cycles in half-cell tests. More importantly, the zinc-air battery with CNS as cathode catalyst delivers an excellent high peak power density of 144 mW cm−2. DFT calculation results show that when N and S are co-doped, the spin density of adjacent carbon atoms can be changed, thereby increasing the CNS's binding energy to oxygen and conductivity. The excellent comprehensive performance of CNS undoubtedly discloses its potential practical application in the energy conversation and storage area. [Display omitted] [ABSTRACT FROM AUTHOR]

• Ultrathin 2D metal-organic frameworks decorated with Pt NPs have been fabricated using an ultrasonication-assisted method. • A "win-win" electron decoration effect has been evidenced on the active sites for both ORR and OER. • Remarkable bifunctional catalytic activity towards ORR and OER with ultralow overpotential gap of 665 mV has been demonstrated. • Excellent performance and durability is achieved in the rechargeable Zinc-air battery assembled with the bifunctional catalyst. To meet the increasing demands for highly active electrocatalysts towards oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), here in this work, a new strategy of synergistic nano-architecture design based on Platinum nanoparticles (Pt NPs) and ultrathin two-dimensional (2D) metal-organic frameworks (MOFs) is developed for bifunctional electrochemical catalysts. Compared with commercial Pt/C and RuO 2 catalysts, remarkable enhancements in activity and durability of both oxygen reduction and oxygen evolution reactions are achieved on our PtNPs@MOFs composite materials, with one of the lowest over-potential gaps (E gap) of 665 mV that has ever been reported. The tests on the assembled Zn-air batteries have revealed promising electrocatalytic performance and practical advantage of our new materials as air cathode catalyst. Both experimental results and theoretical study have confirmed the synergistic effect between Pt NPs and MOF nanosheets through a "win-win" electron structural modification, demonstrating the effectiveness of our strategy in developing effective bifunctional oxygen electrocatalysts for various types of electrochemical devices. [ABSTRACT FROM AUTHOR]

[Display omitted] • Design of the prior PA-resistance electrocatalysts through theoretical calculation. • Discovery of different scaling relationship of the adsorption energy difference of O 2 and H x PO(3-x)- 4 on Pt 3 M(1 1 1) alloy surface. • Pt X Cu as the object for the research of internal mechanism of the potentially high PA resistance property. • Higher PA-resistance performance of Pt 2 Cu compared to the commercial PtC in half-cell and full-cell tests. In high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs), dissociative H 3 PO 4 in cathode will block the active sites of Pt-based electrocatalyst, which thus failure to catalyze the oxygen reduction reaction (ORR). Therefore, the electrocatalysts for the ORR in HT-PEMFCs with high resistance to H 3 PO 4 poisoning are significantly important. Due to the similar bonding structure between H x PO 4 3-x/O 2 and Pt (Pt-O), the design of catalysts which could selectively reduce the adsorption energy of the H 3 PO 4 is urgently needed. In this work, we screen proper H 3 PO 4 resistance electrocatalysts through theoretical calculation based on the adsorption energy difference between H x PO 4 3-x and O 2 as an evaluation criterion. Then, we prepared a series of Pt x Cu catalysts based on the theoretical calculation results and further studied the structure-performance relationship of phosphoric acid-resistant catalysts through combining physical property characterization and electrochemical tests including half-cell and single-cell. The mass activity of Pt 2 Cu/C is 0.51 A/mg Pt , exceeding the DOE's 2020 target of 0.44 A/mg Pt. After add 0.1 M H 3 PO 4 into the HClO 4 electrolyte, the half-wave potential (E 1/2) of Pt 2 Cu/C is only negatively shifted by 47 mV, much lower than 90 mV of TKK Pt/C. Furthermore, the HT-PEMFC with Pt 2 Cu/C in the cathode shows a peak power density of 383.4 mW/cm2, which surpasses that of TKK Pt/C for 231.0 mW/cm2. Our strategy of screening catalysts based on the adsorption energy difference study and further verified by experimental methods provides a promising strategy for the design of practical electrocatalyst in the cathode of HT-PEMFCs. [ABSTRACT FROM AUTHOR]

Iron-nitrogen-carbon (Fe-N-C) catalysts for oxygen reduction reaction (ORR) are promising candidates in fuel cell devices but the poor stability remains a grave challenge. The elimination of demetallation is pivotal for extending the life but still incapable due to the ambiguous mechanism. Herein, we show that the structure of FeN 4 site and its structural evolution during ORR has the significant influence. The end-of-test/in-situ Mössbauer spectroscopy and density functional theory study reveal that D1 mainly contributes to the ORR activity but suffers severe demetallation, which is likely due to the instability of FeN 4 C 8. The faster demetallation during ORR, especially at higher potential, can be attributed to the weaker coordination of FeN 4 induced by oxygenated intermediate and electric field according to ab initio molecular dynamics simulations. Finally, the binding energy of Fe-N bond is introduced to describe the influence of structure and structural evolution and give guidance to the improvement of stability. The influence of structure and structural evolution of active site on the demetallation of Fe-N-C is investigated by the end-of-test/in-situ Mössbauer spectroscopy and ab initio molecular dynamics simulation. [Display omitted] • The demetallation related to the degradation of Fe-N-C for ORR is studied. • The stability and activity of FeN 4 varied by structure are identified. • The effect of structural evolution of FeN 4 on demetallation is determined. • The stability and activity mapping of various active sites is exhibited. [ABSTRACT FROM AUTHOR]

The electronic regulation induces a weak adsorption strength of poisonous CO on active Pd nanoparticles, enabling the improvement of electrocatalytic activity for MOR. [Display omitted] • A synergistic catalyst comprised of Pd single atoms and nanoparticles was prepared. • Pd NPs /Pd-N x @C exhibits superior catalytic performance for MOR in alkaline media. • The EMSI between Pd SAs and matrix boosts the electron transfer at their interface. • The charge migration from Pd nanoparticles to the matrix is suppressed. • The adsorption strength of poisonous CO on the active Pd nanoparticles is weakened. For commercially viable direct methanol fuel cells, electrocatalysts play a crucial role in motivating the sluggish methanol oxidation reaction (MOR) over anode. Unfortunately, the large-scale applications of current MOR catalysts are hampered by their poor tolerance to poisoning and fast activity degradation. Herein, a unique composite catalyst comprised of partial Pd nanoparticles and partial Pd single atoms (Pd NPs /Pd-N x @C) is developed. The as-fabricated catalyst exhibits remarkable activity of 9.45 mA·cm−2 towards MOR in alkaline solution, which is 7.05 and 3.92 times that of commercial Pd/C and nanoparticle type (Pd NPs @C) electrocatalysts, respectively. Impressively, the Pd NPs /Pd-N x @C shows the highest long-time stability with 90.38% and 89.8% of the initial activity retained after 3600 s chronoamperometry (CA) test and 2000 cycles of cyclic voltammetry (CV) measurements with accelerated durability test (ADT), respectively. Combined with high-angle annular darkfield scanning transmission electron microscopy (HAADF-STEM), X-ray adsorption fine structure (XAFS) spectra and X-ray photoelectron spectroscopy (XPS) analyses, the superior performance of Pd NPs /Pd-N x @C can be ascribed to the synergistic effect from the Pd single atoms, N-doped carbon supports and Pd nanoparticles. Notably, the embedded Pd single atoms are liable to transfer electrons to the substrate due to the electronic metal-support interactions (EMSI) and the charge transfer between Pd nanoparticles and carbon supports is suppressed, inducing a weak adsorption strength of poisonous carbonous intermediate species on active Pd nanoparticles and improved poisoning tolerance in MOR process, which is verified by density functional theory (DFT) calculations as well as CO-stripping voltammetry experiments. This work not only contributes the first example of a synergistic catalyst between nanoparticles and single atoms for MOR but also deepens the knowledge on the metal-support interaction. [ABSTRACT FROM AUTHOR]

Abstract: Carbon-supported Pt/PdCo and Pt/Au/PdCo catalysts with a low Pt loading were prepared by a combined underpotential deposition and galvanic replacement route. The X-ray diffraction results show that after annealing in H2/Ar atmosphere, the alloy degree of PdCo is enhanced. The average metal particle size of PdCo/C, PdCo/C-H, Pt/PdCo/C and Pt/Au/PdCo/C, characterized by transmission electron microscopy, is about 2.6, 4.1, 5.3 and 5.5nm, respectively. The electrochemical characterizations show that the Pt/PdCo/C electrocatalyst exhibits a high activity toward the oxygen reduction reaction (ORR) but is unstable in electrochemical environment. After the accelerated aging tests (AAT), the electrochemical surface area (ECSA) for the Pt/PdCo/C catalyst decreases by 48% and the half-wave potential of the ORR polarization curve (E 1/2) shifts 35mV negatively. After decorated by Au, both the catalytic activity and stability of the Pt/PdCo/C catalyst are improved significantly. Compared to Pt/PdCo/C, the E 1/2 for Pt/Au/PdCo/C shifts 22mV toward higher potentials. After the AAT, the ECSA decreases only 26%, and the E 1/2 shifts 13mV negatively for Pt/Au/PdCo/C. The enhanced catalytic activity and stability should be due to the high resistance to be oxidized for Pt and the suppressed OH adsorption on the Au-decorated Pt surface. [Copyright &y& Elsevier]

Atomically dispersed Fe-N-C catalyst is fabricated by a rational designed dual-MOFs strategy for efficient and low-cost DMFC application. • A dual-MOFs strategy is developed for the fabrication of atomically dispersed Fe-N-C catalyst. • The formation mechanism of the atomically dispersed Fe-N-C catalyst is well investigated. • The as-prepared catalyst demonstrates high ORR activity, excellent methanol tolerance and outstanding stability in acids. • The DMFC assembled with atomically dispersed Fe-N-C catalyst exhibits excellent performance. The rational design of highly efficient, low-cost and methanol-tolerant catalysts toward the oxygen reduction reaction (ORR) is urgently desired for the commercialization of direct methanol fuel cells (DMFCs). Herein, a novel Fe-N-C catalyst (ZIF/MIL-10-900) is derived from a mixture of ZIF-8 and MIL-101(Fe) and atomically dispersed FeN 4 structures are confirmed by Mössbauer spectra and X-ray absorption spectroscopy. Study on the pyrolysis procedure reveals that Fe atoms in FeN 4 are from MIL-101(Fe), while ZIF-8 acts as structural support and nitrogen sources. The as-prepared catalyst demonstrates a comparable ORR activity with the commercial Pt/C possessing a half-wave potential (E 1/2) of 0.78 V in acids, in combination with excellent methanol tolerance and stability. One of the highest peak power density of 83 mW cm−2 in DMFC (3 M CH 3 OH) by adopting ZIF/MIL-10-900 as cathode catalyst is obtained, which is 2.8-fold higher than that of the commercial Pt/C in the same operating condition. [ABSTRACT FROM AUTHOR]