Revealing the Role of the Ionomer at the Triple-Phase Boundary in a Proton-Exchange Membrane Water Electrolyzer.

In the anodic catalyst layer of a proton-exchange membrane (PEM) water electrolyzer, the triple-phase boundary (TPB) is mainly distributed on the surface of ultrafine iridium-based catalysts encapsulated by the ionomer within the catalyst-ionomer agglomerate. It is found that the ionomer at the TPB acts as a barrier to mass transport and a buffer for the bubble coverage during the oxygen evolution reaction (OER). The barrier effect can decrease the OER performance of the catalysts inside the agglomerate by ≤23%, while the buffer effect can separate the bubble evolution sites from the OER sites, turning the instant deactivation caused by the bubble coverage into a gradual performance loss caused by local water starvation. However, this local water starvation still deteriorates the catalyst performance because of the affinity of the ionomer surface for bubbles. Introducing additional transport paths into the agglomerate can reduce the barrier effect and regulate the bubble behavior, reducing the overpotential by 0.308 V at 5 A cm-2.

Boosting Bulk Oxygen Transport with Accessible Electrode Nanostructure in Low Pt Loading PEMFCs.

Despite the high potential for reducing carbon emissions and contributing to the future of energy utilization, polymer electrolyte membrane fuel cells (PEMFCs) face challenges such as high costs and sluggish oxygen transport in cathode catalyst layers (CCLs). In this study, the impact of pore size distribution on bulk oxygen transport behavior is explored by introducing nano calcium carbonate of varying particle sizes for pore-forming. Physicochemical characterizations for are employed to examine the electrode structure, while in situ electrochemical measurements are used to scrutinize bulk oxygen transport resistance, effective oxygen diffusivity ( D O 2 eff $D_{{{\mathrm{O}}}_2}^{{\mathrm{eff}}}$ ) and fuel cell performance. Additionally, the CCLs are constructed with aid of Lattice Boltzmann method (LBM) simulations and D O 2 eff $D_{{{\mathrm{O}}}_2}^{{\mathrm{eff}}}$ for CCLs with different pore size distribution are calculated. The findings reveal that D O 2 eff $D_{{{\mathrm{O}}}_2}^{{\mathrm{eff}}}$ initially increases and then decreases as the most probable pore size increases. A "sphere-pipe" model is proposed to describe practical bulk oxygen transport in CCLs, highlighting the significant role of not only the pore size of secondary pores but also the number of primary pores in bulk oxygen transport.

Engineering a Dynamic Solvent-Phobic Liquid Electrolyte Interphase for Long-Life Lithium Metal Batteries.

The heterogeneity, species diversity, and poor mechanical stability of solid electrolyte interphases (SEIs) in conventional carbonate electrolytes result in the irreversible exhaustion of lithium (Li) and electrolytes during cycling, hindering the practical applications of Li metal batteries (LMBs). Herein, this work proposes a solvent-phobic dynamic liquid electrolyte interphase (DLEI) on a Li metal (Li-PFbTHF (perfluoro-butyltetrahydrofuran)) surface that selectively transports salt and induces salt-derived SEI formation. The solvent-phobic DLEI with C-F-rich groups dramatically reduces the side reactions between Li, carbonate solvents, and humid air, forming a LiF/Li3PO4-rich SEI. In situ electrochemical impedance spectroscopy and Ab-initio molecular dynamics demonstrate that DLEI effectively stabilizes the interface between Li metal and the carbonate electrolyte. Specifically, the LiFePO4||Li-PFbTHF cells deliver 80.4% capacity retention after 1000 cycles at 1.0 C, excellent rate capacity (108.2 mAh g-1 at 5.0 C), and 90.2% capacity retention after 550 cycles at 1.0 C in full-cells (negative/positive (N/P) ratio of 8) with high LiFePO4 loadings (15.6 mg cm-2) in carbonate electrolyte. In addition, the 0.55 Ah pouch cell of 252.0 Wh kg-1 delivers stable cycling. Hence, this study provides an effective strategy for controlling salt-derived SEI to improve the cycling performances of carbonate-based LMBs.

Unraveling the Effects of Carbon Corrosion on Oxygen Transport Resistance in Low Pt Loading Proton Exchange Membrane Fuel Cells.

Cost and durability have become crucial hurdles for the commercialization of proton exchange membrane fuel cells (PEMFCs). Although a continuous reduction of Pt loading within the cathode catalyst layers (CCLs) can lead to cost savings, it also increases the oxygen transport resistance, which is further compounded by key material degradation. Hence, a further understanding of the mechanism of significant performance loss due to oxygen transport limitations at the triple phase boundaries (TPBs) during the degradation process is critical to the development of low Pt loading PEMFCs. The present study systematically investigates the impact of carbon corrosion in CCLs on the performance and oxygen transport process of low Pt loading PEMFCs through accelerated stress tests (ASTs) that simulate start-up/shutdown cycling. A decline in peak power density from 484.3 to 251.6 mW cm-2 after 1500 AST cycles demonstrates an apparent performance loss, especially at high current densities. The bulk and local oxygen transport resistances (rbulk and Rlocal) of the pristine cell and after 200, 600, 1000, and 1500 AST cycles are quantified by combining the limiting current method with a dual-layer CCL design. The results show that rbulk increased from 1527 to 1679 s cm-2, Rlocal increased from 0.38 to 0.99 s cm-1, and the local oxygen transport resistance with the normalized Pt surface area (rlocal) exhibited an increase from 18.5 to 32.0 s cm-1, indicating a crucial impact on the structure collapse and changes in the chemical properties of the carbon supports in the CCLs. Further, the interaction between the ionomer and carbon supports during the carbon corrosion process is deeply studied via electrochemical quartz crystal microbalance and molecular dynamics simulations. It is concluded that the oxygen-containing functional groups on the carbon surface could impede the adsorption of ionomers on carbon supports by creating an excessively water-rich layer, which in turn aggravates the formation of ionomer agglomerations within the CCLs. This process ultimately leads to the destruction of the TPBs and hinders the transport of oxygen through the ionomer.

Lithium-Mediated Ammonia Electrosynthesis with Ether-Based Electrolytes.

Ammonia is of great importance in fertilizer production and chemical synthesis. It can also potentially serve as a carbon-free energy carrier for a future hydrogen economy. Motivated by a worldwide effort to lower carbon emissions, ammonia synthesis by lithium-mediated electrochemical nitrogen reduction (LiNR) has been considered as a promising alternative to the Haber-Bosch process. A significant performance improvement in LiNR has been achieved in recent years by exploration of favorable lithium salt and proton donor for the electrolyte recipe, but the solvent study is still in its infancy. In this work, a systematic investigation on ether-based solvents toward LiNR is conducted. The assessments of solvent candidates are built on their conductivity, parasitic reactions, product distribution, and faradaic efficiency. Notably, dimethoxyethane gives the lowest potential loss among the investigated systems, while tetrahydrofuran achieves an outstanding faradaic efficiency of 58.5 ± 6.1% at an ambient pressure. We found that solvent molecules impact the above characteristics by dictating the solvation configurations of conductive ions and inducing the formation of solid electrolyte interphase with different compositions. This study highlights the importance of solvents in the LiNR process and advances the electrolyte optimization for better performance.

Progress and prospects of dealloying methods for energy-conversion electrocatalysis.

Developing hydrogen production and utilization technologies is a promising way to achieve large-scale applications of renewable energy. For both water electrolysis and fuel cell electrode reactions, electrocatalysts are critical to their energy conversion efficiencies. Among the various strategies for improving the performance of electrocatalysts, dealloying has been developed as a commonly used effective post-processing method. It originated from anti-corrosion science and can form metal materials with porous or "skin" nanostructures by selectively dissolving the active components in alloys. There are generally two types of dealloying methods: electrochemical dealloying and chemical dealloying. Electrochemical dealloying is more controllable, while chemical dealloying is simpler and less expensive. In this review, the fundamentals, histories, and progress of dealloying methods for energy conversion electrocatalysis are systematically summarized. Furthermore, current problems and prospects are proposed.

Insight into Oxygen Transport in Solid and High-Surface-Area Carbon Supports of Proton Exchange Membrane Fuel Cells.

Understanding the oxygen transport mechanism through an ionomer film that covered the catalyst surface is essential for reducing local oxygen transport resistance and improving the low Pt-loading proton exchange membrane fuel cell performance. Besides the ionomer material, the carbon supports, upon which ionomers and catalyst particles are dispersed, also play a crucial role in local oxygen transport. Increasing attention has been paid to the effects of carbon supports on local transport, but the detailed mechanism is still unclear. Herein, the local oxygen transports based on conventional solid carbon (SC) and high-surface-area carbon (HSC) supports are investigated by molecular dynamics simulations. It is found that oxygen diffuses through the ionomer film that covered the SC supports via "effective diffusion" and "ineffective diffusion". The former denotes the process by which oxygen diffuses directly from the ionomer surface to the Pt upper surface through small and concentrated regions. In contrast, ineffective diffusion suffers more restrictions by both carbon- and Pt-dense layers, and thus, the oxygen pathways are long and tortuous. The HSC supports exhibit larger transport resistance relative to SC supports due to the existence of micropores. Also, the major transport resistance originates from the carbon-dense layer as it inhibits oxygen from diffusing downward and migrating toward the pore opening, while the oxygen transport inside the pore is facile along the pore's inner surface, which leads to a specific and short diffusion pathway. This work provides insight into oxygen transport behavior with SC and HSC supports, which is the basis for the development of high-performance electrodes with low local transport resistance.

Ultrafine Core@Shell Cu1Au1@Cu1Pd3 Nanodots Synergized with 3D Porous N-Doped Graphene Nanosheets as a High-Performance Multifunctional Electrocatalyst.

Rationally combining designed supports and metal-based nanomaterials is effective to synergize their respective physicochemical and electrochemical properties for developing highly active and stable/durable electrocatalysts. Accordingly, in this work, sub-5 nm and monodispersed nanodots (NDs) with the special nanostructure of an ultrafine Cu1Au1 core and a 2-3-atomic-layer Cu1Pd3 shell are synthesized by a facile solvothermal method, which are further evenly and firmly anchored onto 3D porous N-doped graphene nanosheets (NGS) via a simple annealing (A) process. The as-obtained Cu1Au1@Cu1Pd3 NDs/NGS-A exhibits exceptional electrocatalytic activity and noble-metal utilization toward the alkaline oxygen reduction, methanol oxidation, and ethanol oxidation reactions, showing dozens-fold enhancements compared with commercial Pd/C and Pt/C. Besides, it also has excellent long-term electrochemical stability and electrocatalytic durability. Advanced and comprehensive experimental and theoretical analyses unveil the synthetic mechanism of the special core@shell nanostructure and further reveal the origins of the significantly enhanced electrocatalytic performance: (1) the prominent structural properties of NGS, (2) the ultrasmall and monodispersed size as well as the highly uniform morphology of the NDs-A, (3) the special Cu-Au-Pd alloy nanostructure with an ultrafine core and a subnanometer shell, and (4) the strong metal-support interaction. This work not only develops a facile method for fabricating the special metal-based ultrafine-core@ultrathin-shell nanostructure but also proposes an effective and practical design paradigm of comprehensively and rationally considering both supports and metal-based nanomaterials for realizing high-performance multifunctional electrocatalysts, which can be further expanded to other supports and metal-based nanomaterials for other energy-conversion or environmental (electro)catalytic applications.

Platinum-Based Nanocomposite Pt@BSA as an Efficient Electrochemical Biosensing Interface for Rapid and Ultrasensitive Determination of Folate Receptor-Positive Tumor Cells.

Developing a cytosensing strategy based on electrochemical approaches has attracted wide interest due to the low cost, rapid response, and simple instrumentation. In this work, an electrochemical cytosensor employing the Pt@BSA nanocomposite as the biosensing substrate along with the covalent cross-linking of targeting molecules folic acid (FA) was constructed for highly sensitive determination of folate receptor (FR)-positive tumor cells. The prepared Pt@BSA nanocomposite revealed excellent biocompatibility for cell adhesion and proliferation, which was confirmed by cell viability evaluation using thiazolyl blue tetrazolium bromide (MTT) colorimetric methods. Due to the satisfactory electrical conductivity originating from Pt@BSA and the high binding affinity of FA to FR on the cell surface, an ultrasensitive and specific cytosensing device was designed for rapid and quantitative determination of HeLa cells (a model system) by differential pulse voltammetry (DPV) tests. This proposed cytosensor resulted in a wide HeLa cell determination range of 2.8 × 101-2.8 × 106 cells mL-1 with a low DPV detection limit of 9 cells mL-1. The developed cytosensing approach exhibited highly specific recognition of FR-positive tumor cells, excellent inter-assay reproducibility with a relative standard deviation (RSD) of 4.7%, acceptable intra-assay precision, and favorable storage stability, expanding the application of electrochemical measurement technology in the biomedical field of early detection and diagnosis of cancers.

Electronic and Potential Synergistic Effects of Surface-Doped P-O Species on Uniform Pd Nanospheres: Breaking the Linear Scaling Relationship toward Electrochemical Oxygen Reduction.

Developing efficient oxygen reduction reaction (ORR) electrocatalysts is critical to fuel cells and metal-oxygen batteries, but also greatly hindered by the limited Pt resources and the long-standing linear scaling relationship (LSR). In this study, ∼6 nm and highly uniform Pd nanospheres (NSs) having surface-doped (SD) P-O species are synthesized and evenly anchored onto carbon blacks, which are further simply heat-treated (HT). Under alkaline conditions, Pd/SDP-O NSs/C-HT exhibits respective 8.7 (4.3)- and 5.0 (5.5)-fold enhancements in noble-metal-mass- and area-specific activity (NM-MSA and ASA) compared with the commercial Pd/C (Pt/C). It also possesses an improved electrochemical stability. Besides, its acidic ASA and NM-MSA are 2.9 and 5.1 times those of the commercial Pd/C, respectively, and reach 65.4 and 51.5% of those of the commercial Pt/C. Moreover, it also shows nearly ideal 4-electron ORR pathways under both alkaline and acidic conditions. The detailed experimental and theoretical analyses reveal the following: (1) The electronic effect induced by the P-O species can downshift the surface d-band center to weaken the intermediate adsorptions, thus preserving more surface active sites. (2) More importantly, the potential hydrogen bond between the O atom in the P-O species and the H atom in the hydrogen-containing intermediates can in turn stabilize their adsorptions, thus breaking the ORR LSR toward more efficient ORRs and 4-electron pathways. This study develops a low-cost and high-performance ORR electrocatalyst and proposes a promising strategy for breaking the ORR LSR, which may be further applied in other electrocatalysis.

Evaluation of Electrocatalytic Activity of Noble Metal Catalysts Toward Nitrogen Reduction Reaction in Aqueous Solutions under Ambient Conditions.

Electrochemical nitrogen reduction reaction (NRR) is intensively investigated by researchers for its potential to be the next-generation technology to produce ammonia. Many attempts have been made to explore the possibility of electrochemical ammonia production catalyzed by noble metals. However, the produced ammonia in most reported cases is in ppm level or even lower, which is susceptible to potential contaminants in experiments, leading to fluctuating or even contradictory results. Herein, a rigorous procedure was adopted to systematically evaluated the performance of commercial noble metal nanocatalysts toward NRR. No discernible amount of ammonia was detected in either acidic or alkaline solutions. Further, nitrogen-containing contaminants in catalysts that might cause false positive results were detected and characterized. An effective way to remove pre-existing pollutants by consecutive cyclic voltammetry scan was proposed, helping to obtain reliable and reproducible results.

Lithium-mediated electrochemical nitrogen reduction: Mechanistic insights to enhance performance.

Green synthesis of ammonia by electrochemical nitrogen reduction reaction (NRR) shows great potential as an alternative to the Haber-Bosch process but is hampered by sluggish production rate and low Faradaic efficiency. Recently, lithium-mediated electrochemical NRR has received renewed attention due to its reproducibility. However, further improvement of the system is restricted by limited recognition of its mechanism. Herein, we demonstrate that lithium-mediated NRR began with electrochemical deposition of lithium, followed by two chemical processes of dinitrogen splitting and protonation to ammonia. Furthermore, we quantified the extent to which the freshly deposited active lithium lost its activity toward NRR due to a parasitic reaction between lithium and electrolyte. A high ammonia yield of 0.410 ± 0.038 µg s-1 cm-2 geo and Faradaic efficiency of 39.5 ± 1.7% were achieved at 20 mA cm-2 geo and 10 mA cm-2 geo, respectively, which can be attributed to fresher lithium obtained at high current density.

Interaction of Ammonia with Nafion and Electrolyte in Electrocatalytic Nitrogen Reduction Study.

Ammonia synthesis by electrochemical nitrogen reduction reaction (NRR) is a promising alternative to the Haber-Bosch process. Accurate measurement of produced ammonia requires rigorous criteria, which rely on a deeper understanding of ammonia characteristics. Herein, we systematically investigated the interaction of ammonia with Nafion membrane and electrolyte to reveal factors that may induce deviation in ammonia measurements. We demonstrated desirable characteristics of Nafion membrane as a separator in view of the low adsorption rate and low diffusion rate for ammonia. But one should be aware of the possible contaminants pre-existing in the membrane. It was also observed that the acid electrolyte had a much greater affinity for ammonia compared with base electrolyte. Specifically, the acid electrolyte is more vulnerable to potential ammonia contaminant in the feeding gas, whereas base electrolyte is inclined to lose produced ammonia under a continuous nitrogen flow. The findings provide a deeper understanding of ammonia's behavior in NRR test and help obtain accurate and credible ammonia measurements.

Potential-Dependent Mechanistic Study of Ethanol Electro-oxidation on Palladium.

We herein used the density functional theory (DFT) method and the implicit continuum solvation model to study the potential-dependent mechanism of ethanol oxidation reaction (EOR) on palladium (Pd). Energy evolutions of the EOR on low-index Pd surfaces, including (111), (110), and (100), were obtained as a function of the electrode potential. Moreover, the onset potentials for key intermediates and products were calculated. In addition, the potential range for adsorbed ethanol as the most stable adsorption state for proceeding the EOR was determined to be between 0.15 and 0.78 V via the calculated Pourbaix diagrams when considering hydrogen underpotential deposition and Pd(II) oxide formation as competing reactions. Specifically, the behavior of Pd(111) as the dominating facet decided the overall activity of the EOR with onset potentials to acidic acid/acetate at 0.40 V, to carbon dioxide at 0.71 V, and to oxide formation at 0.78 V. Pd(110) was predicted to exhibit the optimal activity toward the EOR with the lowest onset potentials to both the first dehydrogenation process and carbon dioxide at 0.08 and 0.60 V, respectively. A computational potential-dependent mechanism of the EOR was proposed, which agrees well with the experimental curve of linear sweeping voltammetry on the commercial Pd/C electrocatalyst. Our study suggests that targeted control of products can be tuned with proper overpotential and thus provides a foundation for the future development of EOR electrocatalysts.

Promoting Effects of Au Submonolayer Shells on Structure-Designed Cu-Pd/Ir Nanospheres: Greatly Enhanced Activity and Durability for Alkaline Ethanol Electro-Oxidation.

Rationally engineering the surface physicochemical properties of nanomaterials can improve their activity and durability for various electrocatalytic and energy conversion applications. Cu-Pd/Ir (CPI) nanospheres (NSs) anchored on N-doped porous graphene (NPG) [(CPI NSs/NPG)] have been recently demonstrated as a promising electrocatalyst for the alkaline ethanol oxidation reaction (EOR); to further enhance their electrocatalytic performance, the NPG-supported CPI NSs are coated with Au submonolayer (SML) shells (SMSs), through which their surface physicochemical properties can be tuned. CPI NSs/NPG is prepared by our previously developed method and possesses the special structures of composition-graded Cu1Pd1 and surface-doped Ir0.03. The Au SMSs with designed surface coverages are formed via an electrochemical technology involving incomplete Cu underpotential deposition (UPD) and Au3+ galvanic replacement. A distinctive volcano-type relation between the EOR electrocatalytic activity and the Au-SMS surface coverage for CPI@AuSML NSs/NPG is revealed, and the optimal CPI@Au1/6ML NSs/NPG greatly surpasses commercial Pd/C and CPI NSs/NPG in electrocatalytic activity and noble metal utilization. More importantly, its electrocatalytic durability in 1 h chronoamperometric and 500-cycle potential cycling degradation tests is also significantly improved. According to detailed physicochemical characterizations, electrochemical analyses, and density functional theory calculations, the promoting effects of the Au SMS for enhancing the EOR electrocatalytic activity and durability of CPI NSs/NPG can be mainly attributed to the greatly weakened carbonaceous intermediate bonding and properly increased surface oxidation potential. This work also proposes a versatile and effective strategy to tune the surface physicochemical properties of metal-based nanomaterials via incomplete UPD and metal-cation galvanic replacement for advancing their electrocatalytic and energy conversion performance.

Improving the High-Current-Density Performance of PEMFC through Much Enhanced Utilization of Platinum Electrocatalysts on Carbon.

We report an effective approach to the synthesis of high-content and high-dispersion Pt nanoparticles (NPs) on XC-72 carbon black as a cathode electrocatalyst with improved high-current-density performance in proton exchange membrane fuel cells (PEMFCs). While exceptionally high catalytic activity for oxygen reduction reaction (ORR) was reported based on the rotating disk electrode (RDE) technique, such catalysts do not deliver nearly the same level of performance in PEMFC due to the lack of optimized design of catalyst structures on carbon support. We recently developed a synergistic synthesis method to make exceptionally high-content and finely dispersed Pt catalysts, which showed the highest Pt-electroactive surface area and the highest Pt mass activity for ORR among the electrocatalysts tested. More importantly, the membrane electrode assembly (MEA) made with this catalyst showed excellent performance at current densities higher than 1200 mA cm-2 in a hydrogen-air PEMFC measurement. 195Pt NMR was used to analyze the molecular structures of the metal precursors and to understand the mechanisms of the formation of Pt catalysts at high dispersity and uniformity.

Icosahedral Pt-Ni Nanocrystalline Electrocatalyst: Growth Mechanism and Oxygen Reduction Activity.

Engineering the structure of Pt alloy offers an effective way to the design of high performance electrocatalysts. Herein, we synthesize a sandwich-structured, icosahedral Pt2.1 Ni catalyst through a hot injection method. Its growth involves three steps: 1) burst nucleation of Pt atoms to form a Pt-enriched core, 2) heterogeneous nucleation of Ni atoms onto the Pt core to form a Ni-enriched interlayer, and 3) kinetic controlled growth of a Pt-enriched shell. The Pt-enriched core protects the nanostructure from collapse and mitigates the strain change caused by lattice mismatch, and thus enhances the stability of the structure. The Ni-enriched interlayer induces the electronic modification of the outermost Pt shell, and in turn tunes the activity. The Pt-enriched shell provides more active sites through the exposure of (1 1 1) facets and retards the dissolution of Ni atoms. As a result, this sandwich-structure enables impressive electrocatalytic activity (0.91 mA cm-2 and 0.32 AmgPt-1 @ 0.9 V) and duability.