Monosymmetric Fe-N4 sites enabling durable proton exchange membrane fuel cell cathode by chemical vapor modification.

The limited durability of metal-nitrogen-carbon electrocatalysts severely restricts their applicability for the oxygen reduction reaction in proton exchange membrane fuel cells. In this study, we employ the chemical vapor modification method to alter the configuration of active sites from FeN4 to the stable monosymmetric FeN2+N'2, along with enhancing the degree of graphitization in the carbon substrate. This improvement effectively addresses the challenges associated with Fe active center leaching caused by N-group protonation and free radicals attack due to the 2-electron oxygen reduction reaction. The electrocatalyst with neoteric active site exhibited excellent durability. During accelerated aging test, the electrocatalyst exhibited negligible decline in its half-wave potential even after undergoing 200,000 potential cycles. Furthermore, when subjected to operational conditions representative of fuel cell systems, the electrocatalyst displayed remarkable durability, sustaining stable performance for a duration exceeding 248 h. The significant improvement in durability provides highly valuable insights for the practical application of metal-nitrogen-carbon electrocatalysts.

Single atom sites as CO scavenger to allow for crude hydrogen usage in PEMFC.

Nanosized Pt catalysts are the catalyst-of-choice for proton exchange membrane fuel cell (PEMFC) anode, but are limited by their extreme sensitivity to CO in parts per million (ppm) level, thereby making the use of ultrapure H2 a prerequisite to ensure acceptable performance. Herein, we confront the CO poisoning issue by bringing the Ir/Rh single atom sites to synergistically working with their metallic counterparts. In presence of 1000 ppm CO, the catalyst represents not only undisturbed H2 oxidation reaction (HOR) catalytic behavior in electrochemical cell, but also unparalleled peak power density at 643 mW cm-2 in single cell, 27-fold in mass activity of the best PtRu/C catalysts available. Pre-poisoning experiments and surface-enhanced Raman scattering spectroscopy (SERS) and calculation results in combine suggest the presence of adjacent Ir/Rh single atom sites (SASs) to the nanoparticles (NPs) as the origin for this prominent catalytic behavior. The single sites not only exhibit superb CO oxidation performance by themselves, but can also scavenge the CO adsorbed on approximated NPs via supplying reactive OH* species. We open up a new route here to conquer the formidable CO poisoning issue through single atom and nanoparticle synergistic catalysis, and pave the way towards a more robust PEMFC future.

Operando formation of highly efficient electrocatalysts induced by heteroatom leaching.

Heterogeneous nano-electrocatalysts doped with nonmetal atoms have been studied extensively based on the so-called dopant-based active sites, while little attention has been paid to the stability of these dopants under working conditions. In this work, we reveal significantly, when the redox working potential is too low negatively or too high positively, the active sites based on these dopants actually tend to collapse. It means that some previously observed "remarkable catalytic performance" actually originated from some unknown active sites formed in situ. Take the Bi-F for the CO2RR as an example, results show that the observed remarkable activity and stability were not directly from F-based active sites, but the defective Bi sites formed in situ after the dopant leaching. Such a fact is unveiled from several heteroatom-doped nanocatalysts for four typical reactions (CO2RR, HER, ORR, and OER). This work provides insight into the role of dopants in electrocatalysis.

Intrinsic spin shielding effect in platinum-rare-earth alloy boosts oxygen reduction activity.

Oxygen reduction reactions (ORRs) involve a multistep proton-coupled electron process accompanied by the conversion of the apodictic spin configuration. Understanding the role of spin configurations of metals in the adsorption and desorption of oxygen intermediates during ORRs is critical for the design of efficient ORR catalysts. Herein, a platinum-rare-earth-metal-based alloy catalyst, Pt2Gd, is introduced to reveal the role of spin configurations in the catalytic activity of materials. The catalyst exhibits a unique intrinsic spin reconfiguration because of interactions between the Gd-4f and Pt-5d orbitals. The adsorption and desorption of the oxygen species are optimized by modifying the spin symmetry and electronic structures of the material for increased ORR efficiency. The Pt2Gd alloy exhibits a half-wave potential of 0.95 V and a superior mass activity of 1.5 A·mgPt-1 in a 0.1 M HClO4 electrolyte, as well as higher durability than conventional Pt/C catalysts. Theoretical calculations have proven that the spin shielding effect of Gd pairs increases the spin symmetry of Pt-5d orbitals and adsorption preferences toward spin-polarized intermediates to facilitate ORR. This work clarifies the impact of modulating the intrinsic spin state of Pt through the interaction with the local high spin 4f orbital electrons in rare-earth metals, with the aim of boosting the spin-related oxygen reduction reaction, thus fundamentally contributing to the understanding of new descriptors that control ORR activity.

Customized reaction route for ruthenium oxide towards stabilized water oxidation in high-performance PEM electrolyzers.

The poor stability of Ru-based acidic oxygen evolution (OER) electrocatalysts has greatly hampered their application in polymer electrolyte membrane electrolyzers (PEMWEs). Traditional understanding of performance degradation centered on influence of bias fails in describing the stability trend, calling for deep dive into the essential origin of inactivation. Here we uncover the decisive role of reaction route (including catalytic mechanism and intermediates binding strength) on operational stability of Ru-based catalysts. Using MRuOx (M = Ce4+, Sn4+, Ru4+, Cr4+) solid solution as structure model, we find the reaction route, thereby stability, can be customized by controlling the Ru charge. The screened SnRuOx thus exhibits orders of magnitude lifespan extension. A scalable PEMWE single cell using SnRuOx anode conveys an ever-smallest degradation rate of 53 µV h-1 during a 1300 h operation at 1 A cm-2.

Enhanced Acidic Water Oxidation by Dynamic Migration of Oxygen Species at the Ir/Nb2 O5-x Catalyst/Support Interfaces.

Catalyst/support interaction plays a vital role in catalysis towards acidic oxygen evolution (OER), and the performance reinforcement is currently interpreted by either strain or electron donation effect. We herein report that these views are insufficient, where the dynamic evolution of the interface under potential bias must be considered. Taking Nb2 O5-x supported iridium (Ir/Nb2 O5-x ) as a model catalyst, we uncovered the dynamic migration of oxygen species between IrOx and Nb2 O5-x during OER. Direct spectroscopic evidence combined with theoretical computation suggests these migrations not only regulate the in situ Ir structure towards boosted activity, but also suppress its over-oxidation via spontaneously delivering excessive oxygen from IrOx to Nb2 O5-x . The optimized Ir/Nb2 O5-x thus demonstrated exceptional performance in scalable water electrolyzers, i.e., only need 1.839 V to attain 3 A cm-2 (surpassing the DOE 2025 target), and no activity decay during a 2000 h test at 2 A cm-2 .

Synthesis of Co/CeO2 hetero-particles with abundant oxygen-vacancies supported by carbon aerogels for ORR and OER.

It is highly significant for the fabrication of rechargeable metal-air batteries to develop cost-efficient and high-performance electrocatalysts of bifunctionality for both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Herein, we demonstrate a hybrid composed of CeO2-decorated Co nanoparticles supported on three-dimensionally porous carbon aerogels (Co-CeO2/C aerogels) as a superior bifunctional electrocatalyst. The preparation of Co-CeO2/C aerogels depends on the formation of a novel CeCl3/K3Co(CN)6-chitosan (CS) hydrogel, during which the cyanide groups of K3Co(CN)6 combines the hydroxyls in CS by hydrogen bridges, accompanying with the substitution of chloride groups in CeCl3 by cyanide groups in K3Co(CN)6. The electron spin resonance offers a convincing proof that numerous oxygen vacancies were found in Co-CeO2/C aerogels after the introduction of CeO2. The developed Co-CeO2/C aerogels showed an outstanding electrochemical performance for both OER and ORR in comparsion with RuO2 and Pt/C catalysts in 0.1 M KOH solution. A small overpotential (380 mV) and a low Tafel slope (99 mV dec-1) were observed for OER, while the half-wave potential (0.75 V) and the onset potential (0.92 V) were high for ORR. The superior performance could be put down to the multihole heterostructure, multiple components and abundant oxygen vacancies. It was very helpful for the adsorption and the catalyzation of the reactants and the efficient mass transport of reagent/product. This work paves a neoteric method to synthesize a bifunctional hybrid catalyst with a highly efficient performance of energy conversion and storage.

Proton exchange membrane fuel cells powered with both CO and H2.

The CO electrooxidation is long considered invincible in the proton exchange membrane fuel cell (PEMFC), where even a trace level of CO in H2 seriously poisons the anode catalysts and leads to huge performance decay. Here, we describe a class of atomically dispersed IrRu-N-C anode catalysts capable of oxidizing CO, H2, or a combination of the two. With a small amount of metal (24 µgmetal⋅cm-2) used in the anode, the H2 fuel cell performs its peak power density at 1.43 W⋅cm-2 When operating with pure CO, this catalyst exhibits its maximum current density at 800 mA⋅cm-2, while the Pt/C-based cell ceases to work. We attribute this exceptional catalytic behavior to the interplay between Ir and Ru single-atom centers, where the two sites act in synergy to favorably decompose H2O and to further facilitate CO activation. These findings open up an avenue to conquer the formidable poisoning issue of PEMFCs.

Carbon monoxide powered fuel cell towards H2-onboard purification.

Proton exchange membrane fuel cells (PEMFCs) suffer extreme CO poisoning even at PPM level (<10 ppm), owning to the preferential CO adsorption and the consequential blockage of the catalyst surface. Herein, however, we report that CO itself can become an easily convertible fuel in PEMFC using atomically dispersed Rh catalysts (Rh-N-C). With CO to CO2 conversion initiates at 0 V, pure CO powered fuel cell attains unprecedented power density at 236 mW cm-2, with maximum CO turnover frequency (64.65 s-1, 363 K) far exceeding any chemical or electrochemical catalysts reported. Moreover, this feature enables efficient CO selective removal from H2 gas stream through the PEMFC technique, with CO concentration reduced by one order of magnitude through running only one single cell, while simultaneously harvesting electricity. We attribute such catalytic behavior to the weak CO adsorption and the co-activation of H2O due to the interplay between two adjacent Rh sites.

Ultrasound sonochemical synthesis of amorphous Sb2S3-graphene composites for sodium-ion batteries.

Different from traditional methods, ultrasound sonochemical synthesis can create very special reaction conditions by virtue of the effects of acoustic cavitation. The localized spots in the medium liquids can reach the temperature of ~5000 K, and the pressure of ~1000 bar with the treatment of ultrasonic irradiation. The extreme conditions make it possible to fabricate a series of nanostructured materials with peculiar properties. Herein, we successfully prepared a unique amorphous composite of Sb2S3-graphene via sonochemical method at room temperature. Thanks to the opening frame of ion diffusion channels and higher reversibility in thermodynamics, the amorphous composite displayed superior electrochemical properties in comparison with the crystalline counterpart for sodium-ion batteries. Specifically, the amorphous Sb2S3-graphene composite delivered a first discharge capacity of 1867.1 mAh g-1 and a high reversible capacity of over 880 mAh g-1 after 50 cycles. The nanostructured materials synthesized by ultrasound sonochemical method with unique properties have well prospect in the field of energy storage.

Fundamental understanding of the acidic oxygen evolution reaction: mechanism study and state-of-the-art catalysts.

The oxygen evolution reaction (OER), as the anodic reaction of water electrolysis (WE), suffers greatly from low reaction kinetics and thereby hampers the large-scale application of WE. Seeking active, stable, and cost-effective OER catalysts in acidic media is therefore of great significance. In this perspective, studying the reaction mechanism and exploiting advanced anode catalysts are of equal importance, where the former provides guidance for material structural engineering towards a better catalytic activity. In this review, we first summarize the currently proposed OER catalytic mechanisms, i.e., the adsorbate evolution mechanism (AEM) and lattice oxygen evolution reaction (LOER). Subsequently, we critically review several acidic OER electrocatalysts reported recently, with focus on structure-performance correlation. Finally, a few suggestions on exploring future OER catalysts are proposed.