Binary Solvent Induced Stable Interphase Layer for Ultra-Long Life Sodium Metal Batteries.

Sodium foil, promising for high-energy-density batteries, faces reversibility challenges due to its inherent reactivity and unstable solid electrolyte interphase (SEI) layer. In this study, a stable sodium metal battery (SMB) is achieved by tuning the electrolyte solvation structure through the addition of co-solvent 2-methyl tetrahydrofuran (MTHF) to diglyme (Dig). The introduction of cyclic ether-based MTHF results in increased anion incorporation in the solvation structure, even at lower salt concentrations. Specifically, the anion stabilization capabilities of the environmentally sustainable MTHF co-solvent lead to a contact-ion pair-based solvation structure. Time-of-flight mass spectroscopy analysis reveals that a shift toward an anion-dominated solvation structure promotes the formation of a thin and uniform SEI layer. Consequently, employing a NaPF6-based electrolyte with a Dig:MTHF ratio of 50% (v/v) binary solvent yields an average Coulombic efficiency of 99.72% for 300 cycles in Cu||Na cell cycling. Remarkably, at a C/2 cycling rate, Na||Na symmetric cell cycling demonstrates ultra-long-term stability exceeding 7000 h, and full cells with Na0.44MnO2 as a cathode retain 80% of their capacity after 500 cycles. This study systematically examines solvation structure, SEI layer composition, and electrochemical cycling, emphasizing the significance of MTHF-based binary solvent mixtures for high-performance SMBs.

A Data-Driven Approach to Molten Salt Synthesis of N-Rich Carbon Adsorbents for Selective CO2 Capture.

Applying a design of experiments methodology to the molten salt synthesis of nanoporous carbons enables inverse design and optimization of nitrogen (N)-rich carbon adsorbents with excellent CO2 /N2 selectivity and appreciable CO2 capacity for carbon capture via swing adsorption from dilute gas mixtures such as natural gas combined cycle flue gas. This data-driven study reveals fundamental structure-function relationships between the synthesis conditions, physicochemical properties, and achievable selective adsorption performance of N-rich nanoporous carbons derived from molten salt synthesis for CO2 capture. Taking advantage of size-sieving separation of CO2 (3.30 Å) from N2 (3.64 Å) within the turbostratic nanostructure of these N-rich carbons, while limiting deleterious N2 adsorption in a weaker adsorption site that harms selectivity, enables a large CO2 capacity (0.73 mmol g-1 at 30.4 Torr and 30 °C) with noteworthy concurrent CO2 /N2 selectivity as predicted by the ideal adsorbed solution theory (SIAST = 246) with an adsorbed phase purity of 91% from a simulated gas stream containing only 4% CO2 . Optimized N-rich porous carbons, with good physicochemical stability, low cost, and moderate regeneration energy, can achieve performance for selective CO2 adsorption that competes with other classes of advanced porous materials such as chemisorbing zeolites and functionalized metal-organic frameworks.

In Situ Engineering of Inorganic-Rich Solid Electrolyte Interphases via Anion Choice Enables Stable, Lithium Anodes.

The discovery of liquid battery electrolytes that facilitate the formation of stable solid electrolyte interphases (SEIs) to mitigate dendrite formation is imperative to enable lithium anodes in next-generation energy-dense batteries. Compared to traditional electrolyte solvents, tetrahydrofuran (THF)-based electrolyte systems have demonstrated great success in enabling high-stability lithium anodes by encouraging the decomposition of anions (instead of organic solvent) and thus generating inorganic-rich SEIs. Herein, by employing a variety of different lithium salts (i.e., LiPF6, LiTFSI, LiFSI, and LiDFOB), it is demonstrated that electrolyte anions modulate the inorganic composition and resulting properties of the SEI. Through novel analytical time-of-flight secondary-ion mass spectrometry methods, such as hierarchical clustering of depth profiles and compositional analysis using integrated yields, the chemical composition and morphology of the SEIs generated from each electrolyte system are examined. Notably, the LiDFOB electrolyte provides an exceptionally stable system to enable lithium anodes, delivering >1500 cycles at a current density of 0.5 mAh g-1 and a capacity of 0.5 mAh g-1 in symmetrical cells. Furthermore, Li//LFP cells using this electrolyte demonstrate high-rate, reversible lithium storage, supplying 139 mAh g(LFP) -1 at C/2 (≈0.991 mAh cm-2 , @ 0.61 mA cm-2 ) with 87.5% capacity retention over 300 cycles (average Coulombic efficiency >99.86%).

A Review of Transition Metal Boride, Carbide, Pnictide, and Chalcogenide Water Oxidation Electrocatalysts.

Transition metal borides, carbides, pnictides, and chalcogenides (X-ides) have emerged as a class of materials for the oxygen evolution reaction (OER). Because of their high earth abundance, electrical conductivity, and OER performance, these electrocatalysts have the potential to enable the practical application of green energy conversion and storage. Under OER potentials, X-ide electrocatalysts demonstrate various degrees of oxidation resistance due to their differences in chemical composition, crystal structure, and morphology. Depending on their resistance to oxidation, these catalysts will fall into one of three post-OER electrocatalyst categories: fully oxidized oxide/(oxy)hydroxide material, partially oxidized core@shell structure, and unoxidized material. In the past ten years (from 2013 to 2022), over 890 peer-reviewed research papers have focused on X-ide OER electrocatalysts. Previous review papers have provided limited conclusions and have omitted the significance of "catalytically active sites/species/phases" in X-ide OER electrocatalysts. In this review, a comprehensive summary of (i) experimental parameters (e.g., substrates, electrocatalyst loading amounts, geometric overpotentials, Tafel slopes, etc.) and (ii) electrochemical stability tests and post-analyses in X-ide OER electrocatalyst publications from 2013 to 2022 is provided. Both mono and polyanion X-ides are discussed and classified with respect to their material transformation during the OER. Special analytical techniques employed to study X-ide reconstruction are also evaluated. Additionally, future challenges and questions yet to be answered are provided in each section. This review aims to provide researchers with a toolkit to approach X-ide OER electrocatalyst research and to showcase necessary avenues for future investigation.

Tailoring 3D-Printed Electrodes for Enhanced Water Splitting.

Alkaline water electrolysis, a promising technology for clean energy storage, is constrained by extrinsic factors in addition to intrinsic electrocatalytic activity. To begin to compare between catalytic materials for electrolysis applications, these extrinsic factors must first be understood and controlled. Here, we modify extrinsic electrode properties and study the effects of bubble release to examine how the electrode and surface design impact the performance of water electrolysis. We fabricate robust and cost-effective electrodes through a sequential three-dimensional (3D) printing and metal deposition procedure. Through a systematic assessment of the deposition procedure, we confirm the close relationship between extrinsic electrode properties (i.e., wettability, surface roughness, and electrochemically active surface area) and electrochemical performance. Modifying the electrode geometry, size, and electrolyte flow rate results in an overpotential decrease and different bubble diameters and lifetimes for the hydrogen (HER) and oxygen evolution reactions (OER). Hence, we demonstrate the essential role of the electrode architecture and forced electrolyte convection on bubble release. Additionally, we confirm the suitability of ordered, Ni-coated 3D porous structures by evaluating the HER/OER performance, bubble dissipation, and long-term stability. Finally, we utilize the 3D porous electrode as a support for studying a benchmark NiFe electrocatalyst, confirming the robustness and effectiveness of 3D-printed electrodes for testing electrocatalytic materials while extrinsic properties are precisely controlled. Overall, we demonstrate that tailoring electrode architectures and surface properties result in precise tuning of extrinsic electrode properties, providing more reproducible and comparable conditions for testing the efficiency of electrode materials for water electrolysis.

Camphene-Assisted Fabrication of Free-Standing Lithium-Ion Battery Electrode Composites.

Free-standing electrode (FSE) architectures hold the potential to dramatically increase the gravimetric and volumetric energy density of lithium-ion batteries (LIBs) by eliminating the parasitic dead weight and volume associated with traditional metal foil current collectors. However, current FSE fabrication methods suffer from insufficient mechanical stability, electrochemical performance, or industrial adoptability. Here, we demonstrate a scalable camphene-assisted fabrication method that allows simultaneous casting and templating of FSEs comprising common LIB materials with a performance superior to their foil-cast counterparts. These porous, lightweight, and robust electrodes simultaneously enable enhanced rate performance by improving the mass and ion transport within the percolating conductive carbon pore network and eliminating current collectors for efficient and stable Li+ storage (>1000 cycles in half-cells) at increased gravimetric and areal energy densities. Compared to conventional foil-cast counterparts, the camphene-derived electrodes exhibit ∼1.5× enhanced gravimetric energy density, increased rate capability, and improved capacity retention in coin-cell configurations. A full cell containing both a free-standing anode and cathode was cycled for over 250 cycles with greater than 80% capacity retention at an areal capacity of 0.73 mA h/cm2. This active-material-agnostic electrode fabrication method holds potential to tailor the morphology of flexible, current-collector-free electrodes, thus enabling LIBs to be optimized for high power or high energy density Li+ storage. Furthermore, this platform provides an electrode fabrication method that is applicable to other electrochemical technologies and advanced manufacturing methods.

Calcium Poly(Heptazine Imide): A Covalent Heptazine Framework for Selective CO2 Adsorption.

Potassium poly(heptazine imide) (KPHI) has recently garnered attention as a crystalline carbon nitride framework with considerable photoelectrochemical activity. Here, we report a Ca2+-complexed analogue of PHI: calcium poly(heptazine imide) (CaPHI). Despite similar polymer backbone, CaPHI and KPHI exhibit markedly different crystal structures. Spectroscopic, crystallographic, and physisorptive characterization reveal that Ca2+ acts as a structure-directing agent to transform melon-based carbon nitride to crystalline CaPHI with ordered pore channels, extended visible light absorption, and altered band structure as compared to KPHI. Upon acid washing, protons replace Ca2+ atoms in CaPHI to yield H+/CaPHI and enhance porosity without disrupting crystal structure. Further, these proton-exchanged PHI frameworks exhibit large adsorption affinity for CO2 and exceptional performance for selective carbon capture from dilute streams. Compared to a state-of-the-art metal organic framework, UTSA-16, H+/CaPHI exhibits more than twice the selectivity (∼300 vs ∼120) and working capacity (∼1.2 mmol g-1 vs ∼0.5 mmol g-1) for a feed of 4% CO2 (1 bar, 30 °C).

Transition metal-doped Ni-rich layered cathode materials for durable Li-ion batteries.

Doping is a well-known strategy to enhance the electrochemical energy storage performance of layered cathode materials. Many studies on various dopants have been reported; however, a general relationship between the dopants and their effect on the stability of the positive electrode upon prolonged cell cycling has yet to be established. Here, we explore the impact of the oxidation states of various dopants (i.e., Mg2+, Al3+, Ti4+, Ta5+, and Mo6+) on the electrochemical, morphological, and structural properties of a Ni-rich cathode material (i.e., Li[Ni0.91Co0.09]O2). Galvanostatic cycling measurements in pouch-type Li-ion full cells show that cathodes featuring dopants with high oxidation states significantly outperform their undoped counterparts and the dopants with low oxidation states. In particular, Li-ion pouch cells with Ta5+- and Mo6+-doped Li[Ni0.91Co0.09]O2 cathodes retain about 81.5% of their initial specific capacity after 3000 cycles at 200 mA g-1. Furthermore, physicochemical measurements and analyses suggest substantial differences in the grain geometries and crystal lattice structures of the various cathode materials, which contribute to their widely different battery performances and correlate with the oxidation states of their dopants.

Li-Zn Overlayer to Facilitate Uniform Lithium Deposition for Lithium Metal Batteries.

The highly reactive nature and rough surface of Li foil can lead to the uncontrollable formation of Li dendrites when employed as an anode in a lithium metal battery. Thus, it could be of great practical utility to create uniform, electrochemically stable, and "lithiophilic" surfaces to realize homogeneous deposition of Li. Herein, a LiZn alloy layer is deposited on the surface of Li foil by e-beam evaporation. The idea is to introduce a uniform alloy surface to increase the active area and make use of the Zn sites to induce homogeneous nucleation of Li. The results show that the alloy film protected the Li metal anode, allowing for a longer cycling life with a lower deposition overpotential over a pure-Li metal anode in symmetric Li cells. Furthermore, full cells pairing the modified lithium anode with a LiFePO4 cathode showed an incremental increase in Coulombic efficiency compared with pure-Li. The concept of using only an alloy modifying layer by an in-situ e-beam deposition synthesis method offers a potential method for enabling lithium metal anodes for next-generation lithium batteries.

Anodized Nickel Foam for Oxygen Evolution Reaction in Fe-Free and Unpurified Alkaline Electrolytes at High Current Densities.

To achieve practically high electrocatalytic performance for the oxygen evolution reaction (OER), the active surface area should be maximized without severely compromising electron and mass transport throughout the catalyst electrode. Though the importance of electron and mass transport has been studied using low surface area catalysts under low current densities (∼tens of mA/cm2), the transport properties of large surface area catalysts under high operating current densities (∼500 mA/cm2) for practical OER catalysis have rarely been explored. Herein, three-dimensional (3D) hierarchically porous anodized nickel foams (ANFs) with large and variable surface areas were synthesized via electrochemical anodization of 3D nickel foam and applied as OER electrocatalysts in Fe-free and unpurified KOH electrolytes. Using Fe-free and in situ Fe-doped ANF that were prepared in Fe-free and unpurified electrolytes, respectively, we investigated the interdependent effects of active surface area and transport properties on OER activity under practically high current densities. While activity increased linearly with active surface area for Fe-free ANF, the activity of Fe-doped ANF showed a nonlinear increase with active surface area due to lower electrocatalytic activity enhancement. Detailed investigations on the possible factors (Fe incorporation, mass transport, and electron transport) identified that electron transport limitations played the major role in restricting the activity enhancement with increasing active surface area for Fe-doped ANF, although Fe-doped ANF has electron transport properties better than those of Fe-free ANF. This study exemplifies the growing significance of electron transport properties in large surface area catalysts, especially those with superb intrinsic catalytic activity and high operating current density.

Recent Developments in Dendrite-Free Lithium-Metal Deposition through Tailoring of Micro- and Nanoscale Artificial Coatings.

Forty years after the failed introduction of rechargeable lithium-metal batteries and 30 years after the successful commercialization of the lower capacity, graphite-anode-based lithium-ion battery by Sony, demand for higher energy density batteries is leading to reinvestigation of the problem of dendrite growth that makes the metallic lithium anodes unsafe and prevented commercialization to begin with. One strategy to mitigate dendrite growth is to deposit thin, tailored, corrosion-passivating coatings on the metallic lithium, instead of allowing the metal to spontaneously react with the organic electrolyte solution to form its passivating solid electrolyte interface (SEI). The challenge is to find and to deposit a coating that is electronically insulating yet allows uniform permeation of Li+ at a high cycling rate, such that Li-metal is electrodeposited uniformly on the nanoscale below the tailored coating. Recently, a number of studies have examined multicomponent films, taking advantage of the properties of two different materials, which can be tuned separately or chosen for their complementary properties. Use of these multicomponent coatings will likely enable future researchers to create rationally designed SEIs capable of effectively suppressing the growth of Li dendrites. This review discusses recent developments in micro- and nanoscale tailored coatings to meet that need.

Catalytic Reactions on Pd-Au Bimetallic Model Catalysts.

ConspectusThe enhanced catalytic activity of Pd-Au catalysts originates from ensemble effects related to the local composition of Pd and Au. The study of Pd-Au planar model catalysts in an ultrahigh vacuum (UHV) environment allows the observation of molecular level catalytic reactions between the Pd-Au surface and target molecules. Recently, there has been progress in understanding the behavior of simple molecules (H2, O2, CO, etc.) employing UHV surface science techniques, the results of which can be applied not only to heterogeneous catalysis but also to electro- and photochemical catalysis.Employing UHV methods in the investigation of Pd-Au model catalysts has shown that single Pd atoms can dissociatively adsorb H2 molecules. The recombinative desorption temperature of H2 varies with Pd ensemble size, which allows the use of H2 as a probe molecule for quantifying surface composition. In particular, H2 desorption from Pd-Au interface sites (or small Pd ensembles) is observed from 150-300 K, which is between the H2 desorption temperature from pure Au (∼110 K) and Pd (∼350 K) surfaces. When the Pd ensembles are large enough to form Pd(111)-like islands, H2 desorption occurs from 300-400 K, as with pure Pd surfaces. The different H2 desorption behavior, which depends on Pd ensemble size, has also been applied to the analysis of dehydrogenation mechanisms for potential liquid storage mediums for H2, namely formic acid and ethanol. In both cases, the Pd-Au interface is the main reaction site for generating H2 from formic acid and ethanol with less overall decomposition of the two molecules (compared to pure Pd).The chemistry behind O2 activation has also been informed through the control of Pd ensembles on a gold model catalyst for acetaldehyde and ethanol oxidation reactions under UHV conditions. O2 molecules molecularly adsorbed on continuous Pd clusters can be dissociated into O adatoms above 180 K. This O2 activation process is improved by coadsorbed H2O molecules. It is also possible to directly (through a precursor mechanism) introduce O adatoms on the Pd-Au surface by exposure to O2 at 300 K. The quantity of dissociatively adsorbed O adatoms is proportional to the Pd coverage. However, the O adatoms are more reactive on a less Pd covered surface, especially at the Pd-Au interface sites, which can initiate CO oxidation at temperatures as low as 140 K. Acetaldehyde molecules can be selectively oxidized to acetic acid on the Pd-Au surface with O adatoms, in which the selectivity toward acetic acid originates from preventing the decarboxylation of acetate species. Moreover, the O adatoms on the Pd-Au surface accelerate ethanol dehydrogenation, which causes the increase in acetaldehyde production. Hydrogen is continuously abstracted from the formed acetaldehyde and remaining ethanol molecules, and they ultimately combine as ethyl acetate on the Pd-Au surface.Using Pd-Au model catalysts under UHV conditions allows the discovery of molecular level mechanistic details regarding the catalytic behavior of H and O adatoms with other molecules. We also expect that these findings will be applicable regarding other chemistry on Pd-Au catalysts.

Stabilization of a Highly Ni-Rich Layered Oxide Cathode through Flower-Petal Grain Arrays.

Nickel adds to the capacity of layered oxide cathodes of lithium-ion batteries but comprises their stability. We report a petal-grained Li[Ni0.89Co0.10Sb0.01]O2 cathode that is, nevertheless, stable. The stability originates from the ordering of the nanosized grains in a dense, flower-petal-like array, where the elongated and nearly parallel grains radiate from the center to the surface. The ordering of the grains prevents microcrack generation from abrupt lattice changes of the stressful H2-H3 phase transition. The tight packing of the nanograins is conserved upon cycling, preventing destructive seepage of the electrolytic solution into the particles. The half-cell, cycling between 2.7-4.3 V versus Li/Li+ at a 0.5 C rate retains 95.0% of its initial capacity of 220 mAh g-1 after 100 cycles. The full-cell, cycling with a graphite anode and between 3.0-4.2 V at a 1 C rate, retains 83.9% of its initial capacity after 1000 cycles.

Simultaneous Sulfite Electrolysis and Hydrogen Production Using Ni Foam-Based Three-Dimensional Electrodes.

The electrochemical oxidation of sulfite ions offers encouraging advantages for large-scale hydrogen production, while sulfur dioxide emissions can be effectively used to obtain value-added byproducts. Herein, the performance and stability during sulfite electrolysis under alkaline conditions are evaluated. Nickel foam (NF) substrates were functionalized as the anode and cathode through electrochemical deposition of palladium and chemical oxidation to carry out the sulfite electro-oxidation and hydrogen evolution reactions, respectively. A combined analytical approach in which a robust electrochemical flow cell was coupled to different in situ and ex situ measurements was successfully implemented to monitor the activity and stability during electrolysis. Overall, satisfactory sulfite conversion and hydrogen production efficiencies (>90%) at 10 mA·cm-2 were mainly attributed to the use of NF in three-dimensional electrodes with a large surface area and enhanced mass transfer. Furthermore, stabilization processes associated with electrochemical dissolution and sulfur crossover through the membrane induced specific changes in the chemical and physical properties of the electrodes after electrolysis. This study demonstrates that NF-based electrocatalysts can be incorporated in an efficient electrochemical flow cell system for sulfite electrolysis and hydrogen production, with potential applications at a large scale.

Blade-Type Reaction Front in Micrometer-Sized Germanium Particles during Lithiation.

To investigate the lithium transport mechanism in micrometer-sized germanium (Ge) particles, in situ focused ion beam-scanning electron microscopy was used to monitor the structural evolution of individual Ge particles during lithiation. Our results show that there are two types of reaction fronts during lithiation, representing the differences of reactions on the surface and in bulk. The cross-sectional SEM images and transmission electron microscopy characterizations show that the interface between amorphous LixGe and Ge has a wedge shape because of the higher Li transport rate on the surface of the particle. The blade-type reaction front is formed at the interface of the amorphous LixGe and crystalline Ge and is attributed to the large strain at the interface.

Current Progress and Future Directions in Gas-Phase Metal-Organic Framework Thin-Film Growth.

Deposition of materials as a thin film is important for various applications, such as sensors, microelectronic devices, and membranes. There have been breakthroughs in gas-phase metal-organic framework (MOF) thin-film growth, which is more applicable to micro- and nanofabrication processes and also less harmful to the environment than solvent-based methods. Three different types of gas-phase MOF thin film deposition methods have been developed using chemical vapor deposition (CVD), atomic layer deposition (ALD), and physical vapor deposition (PVD)-CVD combined techniques. The CVD-based method basically converts metal oxide layers into MOF thin films by exposing the surface to ligand vapor. The ALD-based method allows growing MOF thin films following layer-by-layer (LBL) growth by sequentially exposing gas-phase metal and ligand precursors. The PVD-CVD method uses PVD for metal deposition and CVD for ligand deposition, which is similar to LBL growth. These gas-phase growth methods can broaden the use of MOFs in diverse areas. Herein, the current progress of gas-phase MOF thin film growth is discussed and future directions suggested.

Hydrogen desorption from the surface and subsurface of cobalt.

The influence of coverage on the diffusion of hydrogen into the subsurface of cobalt was studied using density functional theory (DFT) and temperature programmed desorption (TPD). DFT calculations show that as the hydrogen coverage on Co(0001) increases, the barrier for hydrogen diffusion into the bulk decreases by 20%. Additionally, subsurface hydrogen on a hydrogen covered surface was found to be more stable when compared to a clean cobalt surface. To test these theoretical findings experimentally, excited hydrogen was used in an ultra-high vacuum environment to access higher hydrogen coverages. Our TPD studies showed that at high hydrogen coverages, a sharp low temperature feature appeared, indicating the stabilization of subsurface hydrogen. Further DFT calculations indicate that this sharp low temperature feature results from associative hydrogen desorption from a hydrogen saturated surface with a population of subsurface hydrogen. Microkinetic modelling was used to model the TPD spectra for hydrogen desporption from cobalt with and without subsurface hydrogen, showing reasonable agreement with experiment.

Lithium Fluoride Coated Silicon Nanocolumns as Anodes for Lithium Ion Batteries.

Silicon (Si) films are promising anode materials in thin-film lithium batteries due to their high capacity of 3578 mAh g-1, but the huge volume expansion of lithiated Li15Si4 and the unstable solid electrolyte interphase (SEI) preclude their practical application. Here lithium fluoride (LiF) coated Si nanocolumns are fabricated by glancing angle evaporation to address the obstacle. The LiF coating can elevate the lithium ion diffusion coefficient (LDC) of Si electrodes upon the alloying reaction and reduce the LDC upon the SEI formation. The composition evolution of the outer SEI layer in the LiF/Si electrodes is studied by ex situ X-ray photoelectron spectroscopy. The modified surface and mitigated volume expansion enable the LiF/Si nanocolumns to exhibit superior rate capability and higher cycling stability compared with the pristine Si nanocolumns. This work demonstrates the positive effect of LiF coating for reducing the polarization and forming a robust SEI film on Si anodes.

Effect of Selenium Content on Nickel Sulfoselenide-Derived Nickel (Oxy)hydroxide Electrocatalysts for Water Oxidation.

An efficient and inexpensive electrocatalyst for the oxygen evolution reaction (OER) must be found in order to improve the viability of hydrogen fuel production via water electrolysis. Recent work has indicated that nickel chalcogenide materials show promise as electrocatalysts for this reaction and that their performance can be further enhanced with the generation of ternary, bimetallic chalcogenides (i.e., Ni1-aMaX2); however, relatively few studies have investigated ternary chalcogenides created through the addition of a second chalcogen (i.e., NiX2-aYa). To address this, we studied a series of Se-modified Ni3S2 composites for use as OER electrocatalysts in alkaline solution. We found that the addition of Se results in the creation of Ni3S2/NiSe composites composed of cross-doped metal chalcogenides and show that the addition of 10% Se reduces the overpotential required to reach a current density of 10 mA/cm2 by 40 mV versus a pure nickel sulfide material. Chemical analysis of the composites' surfaces shows a reduction in the amount of nickel oxide species with Se incorporation, which is supported by transmission electron microscopy; this reduction is correlated with a decrease in the OER overpotentials measured for these samples. Together, our results suggest that the incorporation of Se into Ni3S2 creates a more conductive material with a less-oxidized surface that is more electrocatalytically active and resistant to further oxidation. Importantly, oxidation does still occur, and the active catalyst is most likely a nickel (oxy)hydroxide surrounding a crystalline, conductive Ni3S2-xSex core.

Low temperature dissociation of CO on manganese promoted cobalt(poly).

We observe that metallic manganese alloyed with polycrystalline cobalt promotes the dissociation of CO. Increasing coverages of Mn on Co facillitate stronger molecular CO binding energies and stronger C(ad) + O(ad) binding energies. These findings show the role of metallic manganese in promoting model Co Fischer-Tropsch catalysis.