Pourbaix Machine Learning Framework Identifies Acidic Water Oxidation Catalysts Exhibiting Suppressed Ruthenium Dissolution.

The demand for green hydrogen has raised concerns over the availability of iridium used in oxygen evolution reaction catalysts. We identify catalysts with the aid of a machine learning-aided computational pipeline trained on more than 36,000 mixed metal oxides. The pipeline accurately predicts Pourbaix decomposition energy (Gpbx) from unrelaxed structures with a mean absolute error of 77 meV per atom, enabling us to screen 2070 new metallic oxides with respect to their prospective stability under acidic conditions. The search identifies Ru0.6Cr0.2Ti0.2O2 as a candidate having the promise of increased durability: experimentally, we find that it provides an overpotential of 267 mV at 100 mA cm-2 and that it operates at this current density for over 200 h and exhibits a rate of overpotential increase of 25 µV h-1. Surface density functional theory calculations reveal that Ti increases metal-oxygen covalency, a potential route to increased stability, while Cr lowers the energy barrier of the HOO* formation rate-determining step, increasing activity compared to RuO2 and reducing overpotential by 40 mV at 100 mA cm-2 while maintaining stability. In situ X-ray absorption spectroscopy and ex situ ptychography-scanning transmission X-ray microscopy show the evolution of a metastable structure during the reaction, slowing Ru mass dissolution by 20× and suppressing lattice oxygen participation by >60% compared to RuO2.

Selective reduction of CO to acetaldehyde with CuAg electrocatalysts.

Electrochemical CO reduction can serve as a sequential step in the transformation of CO2 into multicarbon fuels and chemicals. In this study, we provide insights on how to steer selectivity for CO reduction almost exclusively toward a single multicarbon oxygenate by carefully controlling the catalyst composition and its surrounding reaction conditions. Under alkaline reaction conditions, we demonstrate that planar CuAg electrodes can reduce CO to acetaldehyde with over 50% Faradaic efficiency and over 90% selectivity on a carbon basis at a modest electrode potential of -0.536 V vs. the reversible hydrogen electrode. The Faradaic efficiency to acetaldehyde was further enhanced to 70% by increasing the roughness factor of the CuAg electrode. Density functional theory calculations indicate that Ag ad-atoms on Cu weaken the binding energy of the reduced acetaldehyde intermediate and inhibit its further reduction to ethanol, demonstrating that the improved selectivity to acetaldehyde is due to the electronic effect from Ag incorporation. These findings will aid in the design of catalysts that are able to guide complex reaction networks and achieve high selectivity for the desired product.

Bridging Thermal Catalysis and Electrocatalysis: Catalyzing CO2 Conversion with Carbon-Based Materials.

Understanding the differences between reactions driven by elevated temperature or electric potential remains challenging, largely due to materials incompatibilities between thermal catalytic and electrocatalytic environments. We show that Ni, N-doped carbon (NiPACN), an electrocatalyst for the reduction of CO2 to CO (CO2 R), can also selectively catalyze thermal CO2 to CO via the reverse water gas shift (RWGS) representing a direct analogy between catalytic phenomena across the two reaction environments. Advanced characterization techniques reveal that NiPACN likely facilitates RWGS on dispersed Ni sites in agreement with CO2 R active site studies. Finally, we construct a generalized reaction driving-force that includes temperature and potential and suggest that NiPACN could facilitate faster kinetics in CO2 R relative to RWGS due to lower intrinsic barriers. This report motivates further studies that quantitatively link catalytic phenomena across disparate reaction environments.

Engineering Cu surfaces for the electrocatalytic conversion of CO2: Controlling selectivity toward oxygenates and hydrocarbons.

In this study we control the surface structure of Cu thin-film catalysts to probe the relationship between active sites and catalytic activity for the electroreduction of CO2 to fuels and chemicals. Here, we report physical vapor deposition of Cu thin films on large-format (∼6 cm2) single-crystal substrates, and confirm epitaxial growth in the <100>, <111>, and <751> orientations using X-ray pole figures. To understand the relationship between the bulk and surface structures, in situ electrochemical scanning tunneling microscopy was conducted on Cu(100), (111), and (751) thin films. The studies revealed that Cu(100) and (111) have surface adlattices that are identical to the bulk structure, and that Cu(751) has a heterogeneous kinked surface with (110) terraces that is closely related to the bulk structure. Electrochemical CO2 reduction testing showed that whereas both Cu(100) and (751) thin films are more active and selective for C-C coupling than Cu(111), Cu(751) is the most selective for >2e- oxygenate formation at low overpotentials. Our results demonstrate that epitaxy can be used to grow single-crystal analogous materials as large-format electrodes that provide insights on controlling electrocatalytic activity and selectivity for this reaction.

Understanding the Origin of Highly Selective CO2 Electroreduction to CO on Ni,N-doped Carbon Catalysts.

Ni,N-doped carbon catalysts have shown promising catalytic performance for CO2 electroreduction (CO2 R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni-N bonding and correlating CO2 reduction (CO2 R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni,N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO2 R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal-porphyrin catalysts.

Electrochemical flow cell enabling operando probing of electrocatalyst surfaces by X-ray spectroscopy and diffraction.

The rational improvement of current and developing electrochemical technologies requires atomistic understanding of electrode-electrolyte interfaces. However, examining these interfaces under operando conditions, where performance is typically evaluated and benchmarked, remains challenging, as it necessitates incorporating an operando probe during full electrochemical operation. In this study, we describe a custom electrochemical flow cell that enables near-surface-sensitive operando investigation of planar thin-film catalysts at significant hydrogen evolution reaction (HER) rates (in excess of -100 mA cm-2) using grazing incidence X-ray methods. Grazing-incidence X-ray spectroscopy and diffraction were implemented on the same sample under identical HER conditions, demonstrating how the combined measurements track changing redox chemistry and structure of Cu thin-film catalyst surfaces as a function of electrochemical conditions. The coupling of these methods with improved mass transport and hydrodynamic control establishes a new paradigm for operando measurement design, enabling unique insights into the key fundamental processes occurring at the catalyst-electrolyte interface.

Designing Boron Nitride Islands in Carbon Materials for Efficient Electrochemical Synthesis of Hydrogen Peroxide.

Heteroatom-doped carbons have drawn increasing research interest as catalysts for various electrochemical reactions due to their unique electronic and surface structures. In particular, co-doping of carbon with boron and nitrogen has been shown to provide significant catalytic activity for oxygen reduction reaction (ORR). However, limited experimental work has been done to systematically study these materials, and much remains to be understood about the nature of the active site(s), particularly with regards to the factors underlying the activity enhancements of these boron-carbon-nitrogen (BCN) materials. Herein, we prepare several BCN materials experimentally with a facile and controlled synthesis method, and systematically study their electrochemical performance. We demonstrate the existence of h-BN domains embedded in the graphitic structures of these materials using X-ray spectroscopy. These synthesized structures yield higher activity and selectivity toward the 2e- ORR to H2O2 than structures with individual B or N doping. We further employ density functional theory calculations to understand the role of a variety of h-BN domains within the carbon lattice for the ORR and find that the interface between h-BN domains and graphene exhibits unique catalytic behavior that can preferentially drive the production of H2O2. To the best of our knowledge, this is the first example of h-BN domains in carbon identified as a novel system for the electrochemical production of H2O2.

Metal-organic framework-derived bamboo-like nitrogen-doped graphene tubes as an active matrix for hybrid oxygen-reduction electrocatalysts.

In this work, large size (i.e., diameter > 100 nm) graphene tubes with nitrogen-doping are prepared through a high-temperature graphitization process of dicyandiamide (DCDA) and Iron(II) acetate templated by a novel metal-organic framework (MIL-100(Fe)). The nitrogen-doped graphene tube (N-GT)-rich iron-nitrogen-carbon (Fe-N-C) catalysts exhibit inherently high activity towards the oxygen reduction reaction (ORR) in more challenging acidic media. Furthermore, aiming to improve the activity and stability of conventional Pt catalysts, the ORR active N-GT is used as a matrix to disperse Pt nanoparticles in order to build a unique hybrid Pt cathode catalyst. This is the first demonstration of the integration of a highly active Fe-N-C catalyst with Pt nanoparticles. The synthesized 20% Pt/N-GT composite catalysts demonstrate significantly enhanced ORR activity and H(2) -air fuel cell performance relative to those of 20% Pt/C, which is mainly attributed to the intrinsically active N-GT matrix along with possible synergistic effects between the non-precious metal active sites and the Pt nanoparticles. Unlike traditional Pt/C, the hybrid catalysts exhibit excellent stability during the accelerated durability testing, likely due to the unique highly graphitized graphene tube morphologies, capable of providing strong interaction with Pt nanoparticles and then preventing their agglomeration.

A strategy for fabricating nanoporous gold films through chemical dealloying of electrochemically deposited Au-Sn alloys.

We report a novel strategy for the fabrication of nanoporous gold (NPG) films. The fabrication process involves the electrodeposition of a gold-tin alloy, followed by subsequent chemical dealloying of tin. Scanning electron microscopy (SEM) images show a bicontinuous nanoporous structure formed on the substrates after chemical dealloying. Energy dispersive x-ray (EDX) analysis indicates that there are no impurities in the Au-Sn alloy film with an average composition of 58 at. % Au and 42 at. % Sn. After dealloying, only gold remains in the NPG film indicating the effectiveness of this technique. X-ray diffraction (XRD) results reveal that the as-prepared Au-Sn alloy film is composed of two phases (Au5Sn and AuSn), while the NPG film is composed of a single phase (Au). We demonstrate that this approach enables the fabrication of NPG films, either freestanding or supported on various conductive substrates such as copper foil, stainless steel sheet and nickel foam. The resulting NPG electrode exhibits enhanced electrocatalytic activity toward both H2O2 reduction and methanol oxidation compared to the polished Au disc electrode. Our strategy provides a general method to fabricate high quality NPG films on conductive substrates, which will broaden the application potential of NPG or NPG-based materials in various fields such as catalysis, optics and sensor technology.

Multifunctional TiO2-C/MnO2 core-double-shell nanowire arrays as high-performance 3D electrodes for lithium ion batteries.

The unique TiO2-C/MnO2 core-double-shell nanowires are synthesized for the first time using as anode materials for lithium ion batteries (LIBs). They combine both advantages from TiO2 such as excellent cycle stability and MnO2 with high capacity (1230 mA h g(-1)). The additional C interlayer intends to improve the electrical conductivity. The self-supported nanowire arrays grown directly on current-collecting substrates greatly simplify the fabrication processing of electrodes without applying binder and conductive additives. Each nanowire is anchored to the current collector, leading to fast charge transfer. The unique one-dimensional core-double-shell nanowires exhibit enhanced electrochemical performance with a higher discharge/charge capacity, superior rate capability, and longer cycling lifetime.

Redox-Active Phenanthrenequinone Molecules and Nitrogen-Doped Reduced Graphene Oxide as Active Material Composites for Supercapacitor Applications.

Carbon-based supercapacitor electrodes are generally restricted in energy density, as they rely exclusively on electric double-layer capacitance (EDLC). The introduction of redox-active organic molecules to obtain pseudocapacitance is a promising route to develop electrode materials with improved energy densities. In this work, we develop a porous nitrogen-doped reduced graphene oxide and 9,10-phenanthrenequinone composite (N-HtrGO/PQ) via a facile one-step physical adsorption method. The electrochemical evaluation of N-HtrGO/PQ using cyclic voltammetry showed a high capacitance of 605 F g-1 in 1 M H2SO4 when the composite consisted of 30% 9,10-phenanthrenequinone and 70% N-HtrGO. The measured capacitance significantly exceeded pure N-HtrGO without the addition of redox-active molecules (257 F g-1). In addition to promising capacitance, the N-HtrGO/30PQ composite showed a capacitance retention of 94.9% following 20,000 charge/discharge cycles. Based on Fourier transform infrared spectroscopy, we postulate that the strong π-π interaction between PQ molecules and the N-HtrGO substrate enhances the specific capacitance of the composite by shortening pathways for electron transfer while improving structural stability.

Impact of palladium/palladium hydride conversion on electrochemical CO2 reduction via in-situ transmission electron microscopy and diffraction.

Electrochemical conversion of CO2 offers a sustainable route for producing fuels and chemicals. Pd-based catalysts are effective for converting CO2 into formate at low overpotentials and CO/H2 at high overpotentials, while undergoing poorly understood morphology and phase structure transformations under reaction conditions that impact performance. Herein, in-situ liquid-phase transmission electron microscopy and select area diffraction measurements are applied to track the morphology and Pd/PdHx phase interconversion under reaction conditions as a function of electrode potential. These studies identify the degradation mechanisms, including poisoning and physical structure changes, occurring in PdHx/Pd electrodes. Constant potential density functional theory calculations are used to probe the reaction mechanisms occurring on the PdHx structures observed under reaction conditions. Microkinetic modeling reveals that the intercalation of *H into Pd is essential for formate production. However, the change in electrochemical CO2 conversion selectivity away from formate and towards CO/H2 at increasing overpotentials is due to electrode potential dependent changes in the reaction energetics and not a consequence of morphology or phase structure changes.

Highly active and durable core-corona structured bifunctional catalyst for rechargeable metal-air battery application.

A new class of core-corona structured bifunctional catalyst (CCBC) consisting of lanthanum nickelate centers supporting nitrogen-doped carbon nanotubes (NCNT) has been developed for rechargeable metal-air battery application. The nanostructured design of the catalyst allows the core and corona to catalyze the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), respectively. These materials displayed exemplary OER and ORR activity through half-cell testing, comparable to state of the art commercial lanthanum nickelate (LaNiO(3)) and carbon-supported platinum (Pt/C), with added bifunctional capabilities allowing metal-air battery rechargeability. LaNiO(3) and Pt/C are currently the most accepted benchmark electrocatalyst materials for the OER and ORR, respectively; thus with comparable activity toward both of these reactions, CCBC are presented as a novel, inexpensive catalyst component for the cathode of rechargeable metal-air batteries. Moreover, after full-range degradation testing (FDT) CCBC retained excellent activity, retaining 3 and 13 times greater ORR and OER current upon comparison to state of the art Pt/C. Zinc-air battery performances of CCBC is in good agreement with the half-cell experiments with this bifunctional electrocatalyst displaying high activity and stability during battery discharge, charge, and cycling processes. Owing to its outstanding performance toward both the OER and ORR, comparable with the highest performing commercial catalysts to date for each of the respective reaction, coupled with high stability and rechargeability, CCBC is presented as a novel class of bifunctional catalyst material that is very applicable to future generation rechargeable metal-air batteries.

In Situ Studies of Copper-Based CO2 Reduction Electrocatalysts by Scanning Transmission Soft X-ray Microscopy.

A microfluidic-enabled electrochemical device has been developed to investigate electrochemically active nanomaterials under reaction conditions using in situ scanning transmission soft X-ray microscopy (STXM). In situ STXM measurements were conducted on electrodeposited Cu catalysts under electrochemical CO2 reduction (CO2R) conditions. The study provides detailed, quantitative results about the changes in the morphology and chemical structure of the catalytic nanoparticles as a function of applied potentials. The deposited Cu nanoparticles initially contain both Cu(0) and Cu(I). As an increasingly cathodic potential is applied, the Cu(I) species gradually convert to Cu(0) over the potential range of +0.4 to 0 V versus the reversible hydrogen electrode (VRHE). During this process, Cu(I) particles of various sizes are converted to metallic Cu at different reaction rates and at slightly different potentials, indicating a degree of heterogeneity in the electrochemical response of discrete particles. At CO2R relevant potentials, only metallic Cu is observed, and the morphology of the particles is fairly stable within the spatial resolution limits of STXM (∼40 nm). We also report in situ STXM studies of a working electrode with relatively thick Cu-based electrodeposits. The spatially resolved chemical analysis identifies that Cu-oxide species can persist under CO2R conditions, but only when the catalytic nanoparticles are electronically isolated from the working electrode and therefore are catalytically irrelevant. In summary, in situ STXM is presented as a technique to gain advanced morphological and spatially resolved chemical structure insights into electrochemically active nanomaterials, which was used to provide improved understanding regarding Cu nanomaterial catalysts under CO2 reduction conditions.

Tuning Two-Electron Oxygen-Reduction Pathways for H2 O2 Electrosynthesis via Engineering Atomically Dispersed Single Metal Site Catalysts.

The hydrogen peroxide (H2 O2 ) generation via the electrochemical oxygen reduction reaction (ORR) under ambient conditions is emerging as an alternative and green strategy to the traditional energy-intensive anthraquinone process and unsafe direct synthesis using H2 and O2 . It enables on-site and decentralized H2 O2 production using air and renewable electricity for various applications. Currently, atomically dispersed single metal site catalysts have emerged as the most promising platinum group metal (PGM)-free electrocatalysts for the ORR. Further tuning their central metal sites, coordination environments, and local structures can be highly active and selective for H2 O2 production via the 2e- ORR. Herein, recent methodologies and achievements on developing single metal site catalysts for selective O2 to H2 O2 reduction are summarized. Combined with theoretical computation and advanced characterization, a structure-property correlation to guide rational catalyst design with a favorable 2e- ORR process is aimed to provide. Due to the oxidative nature of H2 O2 and the derived free radicals, catalyst stability and effective solutions to improve catalyst tolerance to H2 O2 are emphasized. Transferring intrinsic catalyst properties to electrode performance for viable applications always remains a grand challenge. The key performance metrics and knowledge during the electrolyzer development are, therefore, highlighted.

Chemical Structure and Distribution in Nickel-Nitrogen-Carbon Catalysts for CO2 Electroreduction Identified by Scanning Transmission X-ray Microscopy.

Atomically dispersed metal-nitrogen-carbon (M-N-C) materials are a class of electrocatalysts for fuel cell and electrochemical CO2 reduction (CO2R) applications. However, it is challenging to characterize the identity and concentration of catalytically active species owing to the structural heterogeneity of M-N-C materials. We utilize scanning transmission X-ray microscopy (STXM) as a correlative spectromicroscopy approach for spatially resolved imaging, identification, and quantification of structures and chemical species in mesoscale regions of nickel-nitrogen-carbon (Ni-N-C) catalysts, thereby elucidating the relationship between Ni content/speciation and CO2R activity/selectivity. STXM results are correlated with conventional characterization approaches relying on either bulk average (X-ray absorption spectroscopy) or spatially localized (scanning transmission electron microscopy with electron energy loss spectroscopy) measurements. This comparison illustrates the advantages of soft X-ray STXM to provide spatially resolved identification and quantification of active structures in Ni-N-C catalysts. The active site structures in these catalysts are identified to be atomically dispersed NiN x /C sites distributed throughout entire catalyst particles. The NiN x /C sites were notably demonstrated by spectroscopy to possess a variety of chemical structures with a spectroscopic signature that most closely resembles nickel(II) tetraphenylporphyrin molecules. The quantification and spatial distribution mapping of atomically dispersed Ni active sites achieved by STXM address a target that was elusive to the scientific community despite its importance in guiding advanced material designs.

In Situ Formation of Nano Ni-Co Oxyhydroxide Enables Water Oxidation Electrocatalysts Durable at High Current Densities.

The oxygen evolution reaction (OER) limits the energy efficiency of electrocatalytic systems due to the high overpotential symptomatic of poor reaction kinetics; this problem worsens over time if the performance of the OER electrocatalyst diminishes during operation. Here, a novel synthesis of nanocrystalline Ni-Co-Se using ball milling at cryogenic temperature is reported. It is discovered that, by anodizing the Ni-Co-Se structure during OER, Se ions leach out of the original structure, allowing water molecules to hydrate Ni and Co defective sites, and the nanoparticles to evolve into an active Ni-Co oxyhydroxide. This transformation is observed using operando X-ray absorption spectroscopy, with the findings confirmed using density functional theory calculations. The resulting electrocatalyst exhibits an overpotential of 279 mV at 0.5 A cm-2 and 329 mV at 1 A cm-2 and sustained performance for 500 h. This is achieved using low mass loadings (0.36 mg cm-2 ) of cobalt. Incorporating the electrocatalyst in an anion exchange membrane water electrolyzer yields a current density of 1 A cm-2 at 1.75 V for 95 h without decay in performance. When the electrocatalyst is integrated into a CO2 -to-ethylene electrolyzer, a record-setting full cell voltage of 3 V at current density 1 A cm-2 is achieved.

Direct Integration of Strained-Pt Catalysts into Proton-Exchange-Membrane Fuel Cells with Atomic Layer Deposition.

The design and fabrication of lattice-strained platinum catalysts achieved by removing a soluble core from a platinum shell synthesized via atomic layer deposition, is reported. The remarkable catalytic performance for the oxygen reduction reaction (ORR), measured in both half-cell and full-cell configurations, is attributed to the observed lattice strain. By further optimizing the nanoparticle geometry and ionomer/carbon interactions, mass activity close to 0.8 A mgPt -1 @0.9 V iR-free is achievable in the membrane electrode assembly. Nevertheless, active catalysts with high ORR activity do not necessarily lead to high performance in the high-current-density (HCD) region. More attention shall be directed toward HCD performance for enabling high-power-density hydrogen fuel cells.

Biologically inspired highly durable iron phthalocyanine catalysts for oxygen reduction reaction in polymer electrolyte membrane fuel cells.

In the present work, we have designed and synthesized a new highly durable iron phtalocyanine based nonprecious oxygen reduction reaction (ORR) catalyst (Fe-SPc) for polymer electrolyte membrane fuel cells (PEMFCs). The Fe-SPc, with a novel structure inspired by that of naturally occurring oxygen activation catalysts, is prepared by a nonpyrolyzing method, allowing adequate control of the atomic structure and surface properties of the material. Significantly improved ORR stability of the Fe-SPc is observed compared with the commercial Fe-Pc catalysts. The Fe-SPc has similar activity to that of the commercial Fe-Pc initially, while the Fe-SPc displays 4.6 times higher current density than that of the commercial Fe-Pc after 10 sweep potential cycles, and a current density that is 7.4 times higher after 100 cycles. This has been attributed to the incorporation of electron-donating functional groups, along with a high degree of steric hindrance maintaining active site isolation. Nonprecious Fe-SPc is promising as a potential alternative ORR electrocatalyst for PEMFCs.

Tin-oxide-coated single-walled carbon nanotube bundles supporting platinum electrocatalysts for direct ethanol fuel cells.

Novel tin-oxide (SnO(2))-coated single-walled carbon nanotube (SWNT) bundles supporting platinum (Pt) electrocatalysts for ethanol oxidation were developed for direct ethanol fuel cells. SnO(2)-coated SWNT (SnO(2)-SWNT) bundles were synthesized by a simple chemical-solution route. SnO(2)-SWNT bundles supporting Pt (Pt/SnO(2)-SWNTs) electrocatalysts and SWNT-supported Pt (Pt/SWNT) electrocatalysts were prepared by an ethylene glycol reduction method. The catalysts were physically characterized using TGA, XRD and TEM and electrochemically evaluated through cyclic voltammetry experiments. The Pt/SnO(2)-SWNTs showed greatly enhanced electrocatalytic activity for ethanol oxidation in acid medium, compared to the Pt/SWNT. The optimal SnO(2) loading of Pt/SnO(2)-SWNT catalysts with respect to specific catalytic activity for ethanol oxidation was also investigated.