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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]

[Display omitted] • The effect of structure evolution under working condition of MNC electrocatalysts on the OER activity and stability has been studied with the DFT method. • This work conducted a comprehensive evaluation method for MNC electrocatalysts by taking ΔG *OH as the screening criterion for OER activity and ΔE b of electrocatalysts under working conditions as the stability descriptor. • The stability of MNC electrocatalysts under working conditions, including high temperature, dynamic condition, local electric field and strong specific adsorption has been studied in detail. Developing low-cost, high activity and stability oxygen evolution reaction (OER) catalysts is significantly important but still challenging for water electrolyzers. In this work, we calculated the OER activity and stability of Metal-Nitrogen-Carbon (MNC, M = Co, Ru, Rh, Pd, Ir) based electrocatalyst with different structures (MN 4 C 8 , MN 4 C 10 , MN 4 C 12) using density functional theory (DFT) method. These electrocatalysts were divided into three groups based on the value of ΔG *OH , that is ΔG *OH > 1.53 eV (PdN 4 C 8 , PdN 4 C 10 , PdN 4 C 12), ΔG *OH < 1.23 eV (RuN 4 C 8 , RuN 4 C 10 , RuN 4 C 12 , CoN 4 C 8 , CoN 4 C 10) and 1.23 eV < ΔG *OH < 1.53 eV (RhN 4 C 8 , RhN 4 C 10 , RhN 4 C 12 , IrN 4 C 8 , IrN 4 C 10 , IrN 4 C 12 , CoN 4 C 12), and ΔG *OH determine whether the structure evolution will appear. The results proved that MNC (M = Rh, Ir) with 1.23 eV < ΔG *OH < 1.53 eV shows higher OER activity due to moderate binding energy between reaction intermediates and MNC. Furthermore, these catalysts could maintain M N C structure without further oxidation and structural evolution under working conditions (high temperature, dynamic condition, local electric field and strong specific adsorption), therefore show excellent stability. However, MNC electrocatalyst with ΔG *OH > 1.53 eV or ΔG *OH < 1.23 eV revealed less stability under working conditions, due to their low intrinsic stability or structural evolution under working conditions, respectively. In conclusion, we proposed a comprehensive evaluation method for MNC electrocatalysts by taking ΔG *OH as the screening criterion for OER activity and stability, as well as ΔE b under working condition as descriptor of stability. This is of great significance for the design and screening of ORR, OER and HER electrocatalysts under working conditions. [ABSTRACT FROM AUTHOR]

Abstract: Performance characteristics of a three electrolyte rechargeable acid–alkaline hybrid battery using a PbO2 positive plate and a nickel metal hydride (NiMH x ) negative electrode in separate electrolyte of H2SO4 and KOH were studied. This hybrid battery has three electrolytes in a single cell. A neutral K2SO4 salt solution was placed between the acid and alkaline compartments of the cell, in which a cation exchange membrane and an anion exchange membrane, were employed to separate these three electrolytes. The open circuit voltage of this hybrid cell was found to be 2.64V in an electrolyte configuration of 1M H2SO4|0.2MK2SO4|2M KOH electrolyte configuration, compared to 1.92V in the conventional lead-acid cell in 1M H2SO4 and 1.40V in a NiMH x cell in 2M KOH. This hybrid acid–alkaline PbO2/NiMH x battery was shown to operate with a voltage 20% higher than the conventional lead acid battery and 110% higher than nickel–metal hydride battery at 1/3C discharging rate. The concentrations of the three electrolytes, the dimension of the electrolyte chamber, and other cell/operation parameters with impacts on the hybrid cell performance were investigated. [Copyright &y& Elsevier]

Abstract: Vulcan XC-72R carbon supported Pd nanoparticles was obtained in a NH3-mediated polyol process without any protective agent and characterized by X-ray diffraction (XRD) and transmission electron microscope (TEM) techniques. The added NH3 species is found to have a strong complex ability to Pd, which not only avoids the formation of Pd hydroxide precipitate resulted from Pd hydrolysis, but also restrains the further complete reduction of Pd. Temperature-programmed reduction equipped with a mass spectrometry (TPR-MS) is employed to study the reductive behavior of unreduced Pd complex in Pd/C catalyst and the results show that the post-treatment in a reductive atmosphere at higher temperature is needed to ensure the complete reduction of Pd. XRD patterns show the heat-treated Pd/C sample in a reductive atmosphere has a face centered cubic crystal structure and TEM image indicates that the dispersion of Pd nanoparticles on the carbon support is uniform and in a narrow particle size range. Thermodynamic data analysis is carried out to elucidate the possible reaction pathway for the preparation of Pd/C catalyst in this process. The obtained Pd/C catalyst shows high activity to formic acid oxidation and high selectivity to oxygen reduction reaction (ORR) with the presence of methanol. [Copyright &y& Elsevier]

Abstract: Well dispersed PtSn/C, PtRu/C and Pt/C electrocatalysts were synthesized by a modified polyol process and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and inductively coupled plasma-atomic emission spectrometry techniques. XRD patterns show that Ru induces the contraction of Pt lattice parameter while Sn makes the Pt crystal lattice extended. Ethanol oxidation activities on the catalysts were studied via cyclic voltammetry (CV) and chronoamperometry (CA) methods at room temperature. It is found that the electrode potential plays an important role in the electrochemical behavior of ethanol oxidation on PtRu/C and PtSn/C catalysts. In the lower potential region, PtSn/C possesses higher performance for ethanol oxidation, while in the higher potential region PtRu/C is more active. The different promotion effects of PtSn/C and PtRu/C to ethanol oxidation can be explained by the structural effect and modified bi-functional mechanism in different potential region. Single cell test of a direct ethanol fuel cell (DEFC) was also carried out to elucidate the promotion effect of PtRu/C and PtSn/C catalysts on the ethanol oxidation at 90°C. [Copyright &y& Elsevier]

Abstract: In this study, we present a simple process to obtain highly dispersed palladium nanoparticles on Vulcan XC-72R carbon support without any protective agent. To obtain high metal loading Pd/C catalyst without any surfactant, we modified the polyol process by employing NH3 species as a mediation to control the reaction pathway to avoid the precipitation of Pd(OH)2, and hence the agglomeration of Pd nanoparticles. The obtained Pd/C sample was characterized by X-ray diffraction (XRD) and transmission electron microscope (TEM) techniques. The results show that highly dispersed Pd/C catalyst with an average diameter of 3.0nm could be obtained in this novel process. The activity of formic acid oxidation on this Pd/C catalyst was examined via cyclic voltammetry technique and it is found that the catalytic activity is greatly enhanced due to the reduced particle size and the improved dispersion of palladium nanoparticles on the carbon surface. [Copyright &y& Elsevier]

• The electric field was introduced to WAO system for degradation of isophorone. • TOC removal via WEO process (89.56 %) was much higher than CWAO (75.0 %). • The current efficiency of WEO process (85.6 %) was higher than that of EO (12.1 %). • Synergistic effect was proved to exist in WEO system at optimized conditions. • Fewer intermediates were detected in WEO comparing with the EO and WAO process. How to solve the poisoning and loss of catalysts in catalytic wet air oxidation (CWAO) process remains a great challenge. In this work, an electric field was introduced into wet air oxidation (WAO) process for the efficient degradation of isophorone (IP) wastewater for the first time, named as wet electrocatalytic oxidation (WEO) process. Different composite electrodes including Ti/PbO 2 , Ti/Pt, Ti/Ru-Ir and Ti/Ir-Ta electrode were selected as the anodes of WEO technique and the results showed that the total organic carbon (TOC) removal via WEO process with PbO 2 anode (89.56 %) was much higher than CWAO equipped with noble metal catalyst (Ru/TiZrO 4 , 75.0 %). Additionally, the current efficiency of WEO process was 85.6 %, which was significantly better than that of EO process (12.1 %). A response surface methodology was applied to elucidate the effects of reaction conditions on IP degradation. Analysis of response surface model showed TOC removal were markedly affected (p ≤ 0.01) by the reaction time (t), temperature (T), current density (I D), T2 and I D 2 , and also determined (p ≤ 0.05) by the interactions of T with t and I D respectively. In addition, a synergistic effect was proved to take place in WEO process with synergistic effect factor f of 1.2 at optimized conditions. As an advanced wastewater treatment technology, WEO integrates the advantages of both electro-catalytic oxidation (EO) and WAO. [ABSTRACT FROM AUTHOR]

The strain effect on oxygen reduction reaction (ORR) activity and stability of FeNC electrocatalysts has been studied using density functional theory in this work. Based on the reaction free energy results, the rate-determining step (RDS) of ORR on FeNC is *OH → H2O, and the reaction proceeds with the pathway O2 → *OOH → *O → *OH → H2O on the Fe site. Tensile stress is favorable to enhance the ORR activity, and the highest ORR activity is obtained on the 6%-FeNC electrocatalyst. On the other hand, when the whole oxygen reduction process needs synergy between Fe and adjacent C atoms and proceeds with the pathway O2 → *OOH → *TS → *O & #OH → *O → *OH → H2O, the applied stress will decrease the ORR activity of the FeNC electrocatalyst. We further constructed a Cu@FeNC core–shell model to simulate strained FeNC. However, the adsorption energy of ORR intermediates on Cu@FeNC (1.9%-FeNC) is much weaker than on the corresponding 2%-FeNC, mainly due to the coordination between the Cu substrate and Fe atom. In addition, the formation energy and binding energy indicate that neither tensile nor compressive stress is conducive to the stability of the FeNC electrocatalyst. In summary, tensile stress could enhance the ORR activity of FeNC electrocatalysts when ORR occurs on the Fe atom only. What's more, we should pay more attention to the influence of interface interaction if utilizing a M@FeNC model to achieve strained FeNC. [ABSTRACT FROM AUTHOR]

Carbon-supported Ir3Sn/C and Ir/C catalysts were simply prepared with NaBH4 as a reducing agent under the protection of ethylene glycol at room temperature. TEM and X-ray diffraction (XRD) data showed that the catalysts with small particle size exhibited the typical characteristic of a crystalline Ir fcc structure. Their electrocatalytic activities in comparison with Pt/C and Pt3Sn/C catalysts also prepared by the NaBH4 reduction process were characterized by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperometry (CA) techniques. The results indicated that Ir-based catalysts showed superior electrocatalytic activity towards ethanol oxidation to Pt/C and Pt3Sn/C catalysts, mainly in the low potential region. During single-cell tests at 90°C, better performances of Ir-based catalysts as anodes were obtained compared to that of Pt/C catalyst. The comparable overall performance of Ir3Sn/C to Pt3Sn/C makes it a promising alternative choice of anode catalyst for direct ethanol fuel cells. [Copyright &y& Elsevier]

Abstract: Carbon-supported Ir3Sn/C and Ir/C catalysts were simply prepared with NaBH4 as a reducing agent under the protection of ethylene glycol at room temperature. TEM and X-ray diffraction (XRD) data showed that the catalysts with small particle size exhibited the typical characteristic of a crystalline Ir fcc structure. Their electro-catalytic activities in comparison with Pt/C and Pt3Sn/C catalysts also prepared by the NaBH4 reduction process were characterized by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperometry (CA) techniques. The results indicated that Ir-based catalysts showed superior electro-catalytic activity towards ethanol oxidation to Pt/C and Pt3Sn/C catalysts, mainly at low potential region. During single-cell tests at 90°C, better performances of Ir-based catalysts as anodes were obtained compared to that of Pt/C catalyst. The comparable overall performance of Ir3Sn/C to Pt3Sn/C makes it a promising alternative choice of anode catalyst for direct ethanol fuel cells. [Copyright &y& Elsevier]

Pt–Fe/C catalysts were prepared by a modified polyol synthesis method in an ethylene glycol (EG) solution, and then were heat-treated under H2/Ar (10 vol.%) at moderate temperature (300 °C, Pt–Fe/C300) or high temperature (900 °C, Pt–Fe/C900). As comparison, Pt–Fe/C alloy catalyst was prepared by a two-step method (Pt–Fe/C900B). X-ray diffraction (XRD) and transmission electron microscopy (TEM) images show that particles size of the catalyst increases with the increase of treatment temperatures. Pt–Fe/C300 catalyst has a mean particle size of 2.8 nm (XRD), 3.6 nm (TEM) and some Pt–Fe alloy was partly formed in this sample. Pt–Fe/C900B catalyst has the biggest particle size of 6.2 nm (XRD) and the best Pt–Fe alloy form. Cyclicvoltammetry (CV) shows that Pt–Fe/C300 has larger electrochemical surface area than other Pt–Fe/C and the highest utilization ratio of 76% among these Pt-based catalysts. Rotating disk electrode (RDE) cathodic curves show that Pt–Fe/C300 has the highest oxygen reduction reaction (ORR) mass activity (MA) and specific activity (SA), as compared with Pt/C catalyst in 1.0 M HClO4. However, Pt–Fe/C catalyst does not appears to be a more active catalyst than Pt/C for ORR in 1.0 M HClO4 + 0.1 M CH3OH. Pt–Fe/C300 exhibits higher ORR activity and better performance than other Pt–Fe/C or Pt/C catalysts when employed for cathode in direct methanol single cell test, the enhancement of the cell performance is logically attributed to its higher ORR activity, which is probably attributed to more Pt0 species existing and Fe ion corrosion from the catalyst. [Copyright &y& Elsevier]

[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]

Abstract: Potential-scan tests were conducted to evaluate the stability of a PtRu/C electrocatalyst at anode potentials in a direct methanol fuel cell (DMFC). The results show that, under normal operating conditions, the anode potential in a DMFC is benign for the PtRu/C electrocatalyst. But in the case of deep discharge or short circuit, the anode potential value may exceed 0.6V versus DHE, which is harmful to the PtRu/C electrocatalyst. The dissolution of catalyst components results in an enhanced ohmic resistance and a lowered catalytic activity for methanol electro-oxidation. [Copyright &y& Elsevier]

Abstract: Carbon supported PtSn alloy and PtSnO x particles with nominal Pt:Sn ratios of 3:1 were prepared by a modified polyol method. High resolution transmission electron microscopy (HRTEM) and X-ray microchemical analysis were used to characterize the composition, size, distribution, and morphology of PtSn particles. The particles are predominantly single nanocrystals with diameters in the order of 2.0–3.0nm. According to the XRD results, the lattice constant of Pt in the PtSn alloy is dilated due to Sn atoms penetrating into the Pt crystalline lattice. While for PtSnO x nanoparticles, the lattice constant of Pt only changed a little. HRTEM micrograph of PtSnO x clearly shows that the change of the spacing of Pt (111) plane is neglectable, meanwhile, SnO2 nanoparticles, characterized with the nominal 0.264nm spacing of SnO2 (101) plane, were found in the vicinity of Pt particles. In contrast, the HRTEM micrograph of PtSn alloy shows that the spacing of Pt (111) plane extends to 0.234nm from the original 0.226nm. High resolution energy dispersive X-ray spectroscopy (HR-EDS) analyses show that all investigated particles in the two PtSn catalysts represent uniform Pt/Sn compositions very close to the nominal one. Cyclic voltammograms (CV) in sulfuric acid show that the hydrogen ad/desorption was inhibited on the surface of PtSn alloy compared to that on the surface of the PtSnO x catalyst. PtSnO x catalyst showed higher catalytic activity for ethanol electro-oxidation than PtSn alloy from the results of chronoamperometry (CA) analysis and the performance of direct ethanol fuel cells (DEFCs). It is deduced that the unchanged lattice parameter of Pt in the PtSnO x catalyst is favorable to ethanol adsorption and meanwhile, tin oxide in the vicinity of Pt nanoparticles could offer oxygen species conveniently to remove the CO-like species of ethanolic residues to free Pt active sites. [Copyright &y& Elsevier]

A series of 40 wt.% Pt/C electrocatalysts were prepared by a modified polyol process and an improved aqueous impregnation method with different impregnation time. The characterization results of TEM and XRD identically reveal that the size and distribution of Pt nanoparticles on carbon are controllable by modifying impregnation time in both routes. High dispersion of Pt nanoparticles on carbon is achieved by both methods with 15 min impregnation, while aggregation of Pt nanoparticles takes place with prolonging the impregnation time to 36 h, especially in the aqueous impregnation procedure. UV–vis spectroscopy measurements verified that the redox reaction between PtCl62- and formaldehyde could take place at a slow rate under ambient conditions via a two-step reaction path, where PtCl42- serves as an intermediate. On the other hand, PtCl62- anion can be directly reduced to Pt0 above 333 K in the modified polyol process through an autocatalytic pathway. The short-time-impregnated 40 wt.% Pt/C as cathode electrocatalysts in direct methanol fuel cell performs better than that of long-time-impregnated electrocatalysts. Experimental evidence provides clues for fundamental understanding of elementary steps of the redox reactions, which helps guiding the design and preparation of highly dispersed Pt catalyst with high metal loadings for fuel cells. [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]