A completely precious metal-free alkaline fuel cell with enhanced performance using a carbon-coated nickel anode.

SignificanceWe present a groundbreaking advance in completely nonprecious hydrogen fuel cell technologies achieving a record power density of 200 mW/cm2 with Ni@CNx anode and Co-Mn cathode. The 2-nm CNx coating weakens the O-binding energy, which effectively mitigates the undesirable surface oxidation during hydrogen oxidation reaction (HOR) polarization, leading to a stable fuel cell operation for Ni@CNx over 100 h at 200 mA/cm2, superior to a Ni nanoparticle counterpart. Ni@CNx exhibited a dramatically enhanced tolerance to CO relative to Pt/C, enabling the use of hydrogen gas with trace amounts of CO, critical for practical applications. The complete removal of precious metals in fuel cells lowers the catalyst cost to virtually negligible levels and marks a milestone for practical alkaline fuel cells.

Optical method for quantifying the potential of zero charge at the platinum-water electrochemical interface.

When an electrode contacts an electrolyte, an interfacial electric field forms. This interfacial field can polarize the electrode's surface and nearby molecules, but its effect can be countered by an applied potential. Quantifying the value of this countering potential ('potential of zero charge' (pzc)) is, however, not straightforward. Here we present an optical method for determining the pzc at an electrochemical interface. Our approach uses phase-sensitive second-harmonic generation to determine the electrochemical potential where the interfacial electric field vanishes at an electrode-electrolyte interface with Pt-water as a model experiment. Our method reveals that the pzc of the Pt-water interface is 0.23 ± 0.08 V versus standard hydrogen electrode (SHE) and is pH independent from pH 1 to pH 13. First-principles calculations with a hybrid explicit-implicit solvent model predict the pzc of the Pt(111)-water interface to be 0.23 V versus SHE and reveal how the interfacial water structure rearranges as the electrode potential is moved above and below the pzc. We further show that pzc is sensitive to surface modification; deposition of Ni on Pt shifts the interfacial pzc in the cathodic direction by ~360 mV. Our work demonstrates a materials-agnostic approach for quantifying the interfacial electrical field and water orientation at an electrochemical interface without requiring probe molecules and confirms the long-held view that the interfacial electric field is more intense during hydrogen electrocatalysis in alkaline than in acid.

Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies.

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.

Solution-Phase Synthesis of PdH0.706 Nanocubes with Enhanced Stability and Activity toward Formic Acid Oxidation.

Palladium is one of the few metals capable of forming hydrides, with the catalytic properties being dependent on the elemental composition and spatial distribution of H atoms in the lattice. Herein, we report a facile method for the complete transformation of Pd nanocubes into a stable phase made of PdH0.706 by treating them with aqueous hydrazine at a concentration as low as 9.2 mM. Using formic acid oxidation (FAO) as a model reaction, we systematically investigated the structure-catalytic property relationship of the resultant nanocubes with different degrees of hydride formation. The current density at 0.4 V was enhanced by four times when the nanocubes were completely converted from Pd to PdH0.706. On the basis of a set of slab models with PdH(100) overlayers on Pd(100), we conducted density functional theory calculations to demonstrate that the degree of hybrid formation could influence both the activity and selectivity toward FAO by modulating the relative stability of formate (HCOO) and carboxyl (COOH) intermediates. This work provides a viable strategy for augmenting the performance of Pd-based catalysts toward various reactions without altering the loading of this scarce metal.

Author Correction: Eliminating dissolution of platinum-based electrocatalysts at the atomic scale.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Eliminating dissolution of platinum-based electrocatalysts at the atomic scale.

A remaining challenge for the deployment of proton-exchange membrane fuel cells is the limited durability of platinum (Pt) nanoscale materials that operate at high voltages during the cathodic oxygen reduction reaction. In this work, atomic-scale insight into well-defined single-crystalline, thin-film and nanoscale surfaces exposed Pt dissolution trends that governed the design and synthesis of durable materials. A newly defined metric, intrinsic dissolution, is essential to understanding the correlation between the measured Pt loss, surface structure, size and ratio of Pt nanoparticles in a carbon (C) support. It was found that the utilization of a gold (Au) underlayer promotes ordering of Pt surface atoms towards a (111) structure, whereas Au on the surface selectively protects low-coordinated Pt sites. This mitigation strategy was applied towards 3 nm Pt3Au/C nanoparticles and resulted in the elimination of Pt dissolution in the liquid electrolyte, which included a 30-fold durability improvement versus 3 nm Pt/C over an extended potential range up to 1.2 V.

Growth of sub-nanometric palladium clusters on boron nitride nanotubes: a DFT study.

A QM/MM investigation is reported dealing with the nucleation and growth of small palladium clusters, up to Pd8, on the outer surface of a suitable model of boron nitride nanotubes (BNNTs). It is shown that BNNTs could have a template effect on the cluster growth, which is due to the interplay between Pd-N and Pd-Pd interactions as well as due to the matching of the B3N3 ring and the Pd(111) face arrangement. The values for the cluster adsorption energies reveal a relatively strong physisorption, which suggests that under particular conditions the BNNTs could be used as supports for the preparation of shape-controlled metal clusters.

Bismuthene for highly efficient carbon dioxide electroreduction reaction.

Bismuth (Bi) has been known as a highly efficient electrocatalyst for CO2 reduction reaction. Stable free-standing two-dimensional Bi monolayer (Bismuthene) structures have been predicted theoretically, but never realized experimentally. Here, we show the first simple large-scale synthesis of free-standing Bismuthene, to our knowledge, and demonstrate its high electrocatalytic efficiency for formate (HCOO-) formation from CO2 reduction reaction. The catalytic performance is evident by the high Faradaic efficiency (99% at -580 mV vs. Reversible Hydrogen Electrode (RHE)), small onset overpotential (<90 mV) and high durability (no performance decay after 75 h and annealing at 400 °C). Density functional theory calculations show the structure-sensitivity of the CO2 reduction reaction over Bismuthene and thicker nanosheets, suggesting that selective formation of HCOO- indeed can proceed easily on Bismuthene (111) facet due to the unique compressive strain. This work paves the way for the extensive experimental investigation of Bismuthene in many different fields.

Author Correction: Bismuthene for highly efficient carbon dioxide electroreduction reaction.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.