Ab Initio-Based Kinetic Modeling for the Design of Molecular Catalysts: The Case of H 2 Production Electrocatalysts
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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Transition Metal Nitrides as Promising Catalyst Supports for Tuning CO/H 2 Syngas Production from Electrochemical CO 2 Reduction
The electrochemical carbon dioxide reduction reaction (CO 2 RR) to produce synthesis gas (syngas) with tunable CO/H 2 ratios has been studied by supporting Pd catalysts on transition metal nitride (TMN) substrates. Combining experimental measurements and density functional theory (DFT) calculations, Pd-modified niobium nitride (Pd/NbN) is found to generate much higher CO and H 2 partial current densities and greater CO Faradaic efficiency than Pd-modified vanadium nitride (Pd/VN) and commercial Pd/C catalysts. In-situ X-ray diffraction identifies the formation of PdH in Pd/NbN and Pd/C under CO 2 RR conditions, whereas the Pd in Pd/VN is not fully transformed into the active PdH phase. DFT calculations show that the stabilized *HOCO and weakened *CO intermediates on PdH/NbN are critical to achieving higher CO 2 RR activity. This work suggests that NbN is a promising substrate to modify Pd, resulting in an enhanced electrochemical conversion of CO 2 to syngas with a potential reduction in precious metal loading.
25 ENERGY STORAGE↗
High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting
The search for active, stable, and cost-efficient electrocatalysts for hydrogen production via water splitting could make a substantial impact on energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high-surface-area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction and oxygen evolution reaction compared to Rh/C and Pt/C catalysts. The atomic structure of the Rh2P NCs was directly observed by annular dark-field scanning transmission electron microscopy, which revealed a phosphorus-rich outermost atomic layer. Combined experimental and computational studies suggest that surface phosphorus plays a crucial role in determining the robust catalyst properties.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Designing the Nanoconfined Environment for Energy-Efficient Metal Nanoparticle/Ligand-Based Electrocatalysts
Nanoconfined electrocatalysts demonstrate enhanced selectivity and activity owing to new phenomena emerging from chemical species confined at the interface. Creating these nanoconfined pockets at the interface is not trivial. We need highly negative potentials to create the pockets in metal/ligand catalysts like Ag-nanoparticle/ordered ligand interlayer catalysts. Lowering this activation potential can make the electrocatalysis more energy-efficient, and changes in the environment can impact this potential. We used Density Functional Theory (DFT) to evaluate the impact of ligand length and density, interfacial protons, and surface defects like Ag vacancies and Cu and Au dopants. The nanoconfined configuration is stabilized when the ligands are longer and more densely packed, leading to better agglomeration. It is also stabilized when the ligands adsorb protons and when the ligands detach from the surface easily owing to lower charge transfer. Au-doped surfaces displayed the lowest charge transfer and decreased the activation potential.
Jana, Asmita↗
Perovskite Catalysts for Pure-Water-Fed Anion-Exchange-Membrane Electrolyzer Anodes: Co-design of Electrically Conductive Nanoparticle Cores and Active Surfaces
Anion-exchange-membrane water electrolyzers (AEMWEs) are a possible low-capital-expense, efficient, and scalable hydrogen-production technology with inexpensive hardware, earth-abundant catalysts, and pure water. However, pure-water-fed AEMWEs remain at an early stage of development and suffer from inferior performance compared with proton-exchange-membrane water electrolyzers (PEMWEs). One challenge is to develop effective non-platinum-group-metal (non-PGM) anode catalysts and electrodes in pure-water-fed AEMWEs. We show how LaNiO3-based perovskite oxides can be tuned by cosubstitution on both A- and B-sites to simultaneously maintain high metallic electrical conductivity along with a degree of surface reconstruction to expose a stable Co-based active catalyst. The optimized perovskite, Sr0.1La0.9Co0.5Ni0.5O3, yielded pure-water AEMWEs operating at 1.97 V at 2.0 A cm-2 at 70 °C with a pure-water feed, thus illustrating the utility of the catalyst design principles.
Zhai, Tingting↗
High-performance bifunctional porous non-noble metal phosphide catalyst for overall water splitting
Water electrolysis is an advanced energy conversion technology to produce hydrogen as a clean and sustainable chemical fuel, which potentially stores the abundant but intermittent renewable energy sources scalably. Since the overall water splitting is an uphill reaction in low efficiency, innovative breakthroughs are desirable to greatly improve the efficiency by rationally designing non-precious metal-based robust bifunctional catalysts for promoting both the cathodic hydrogen evolution and anodic oxygen evolution reactions. We report a hybrid catalyst constructed by iron and dinickel phosphides on nickel foams that drives both the hydrogen and oxygen evolution reactions well in base, and thus substantially expedites overall water splitting at 10 mA cm –2 with 1.42 V, which outperforms the integrated iridium (IV) oxide and platinum couple (1.57 V), and are among the best activities currently. Especially, it delivers 500 mA cm –2 at 1.72 V without decay even after the durability test for 40 h, providing great potential for large-scale applications.
08 HYDROGEN↗
Catalysts Prepared from Atomically Dispersed Ce(III) on MgO Rival Bulk Ceria for CO Oxidation
Atomically dispersed cerium catalysts on an inert, crystalline MgO powder support were prepared by using both Ce(III) and Ce(IV) precursors. The materials were used as catalysts for CO oxidation in a once-through flow reactor and characterized by atomic-resolution scanning transmission electron microscopy, X-ray absorption near edge structure spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed reduction, among other techniques, before and after catalysis. The most active catalysts, formed from the precursor incorporating Ce(III), displayed a performance similar to that reported for bulk ceria under comparable conditions. The catalyst provided stable time-on-stream performance for as long as it was kept on stream, two days, increasing slightly in activity as the atomically dispersed cerium ions were transformed into ceria nanodomains represented as CeO x and having increased reducibility on the MgO support. Furthermore, the results suggest how highly dispersed supported ceria catalysts with low cerium loadings can be prepared and may pave the way to improved efficiencies of cerium utilization in oxidation catalysis.
36 MATERIALS SCIENCE↗
Carbon Fiber Reinforced Epoxy Vitrimer: Robust Mechanical Performance and Facile Hydrothermal Decomposition in Pure Water
Conventional carbon fiber reinforced thermosetting polymers (CFRPs) are neither recyclable nor repairable due to their crosslinked network. The rapid growing CFRP market raises a serious concern of the waste management. In this work, a viable method to develop a readily recyclable CFRP based on epoxy vitrimer is introduced. First, a self-catalytic epoxy prepolymer with built-in hydroxy and tertiary amine groups is designed, which upon reaction with an anhydride formed a catalyst-free epoxy vitrimer. The epoxy prepolymer is synthesized from a diamine and an excess of bisphenol A epoxy resin. The hydroxyls and tertiary amines of the epoxy prepolymer efficiently catalyze both curing and the dynamic transesterification of the crosslinked polymer without the need of a catalyst. Then, the epoxy vitrimer is used as the matrix resin to prepare CFRP. The resulting CFRP exhibited a tensile strength as high as 356 MPa. More interestingly, the matrix of the CFRP is efficiently degraded in pure water at above 160 °C. This is because the built-in tertiary amines catalyze the hydrolysis of the ester bonds of the crosslinked network. The simple method developed in this work provides a framework for the development of recyclable CFRP.
Liu, Tuan↗
Selective Oxidation of Lignin Model Compounds
Lignin, the planet's most abundant renewable source of aromatic compounds, is difficult to degrade efficiently to welldefined aromatics. We developed a microwave-assisted catalytic Swern oxidation system using an easily prepared catalyst, MoO 2 Cl 2 (DMSO) 2 , and DMSO as the solvent and oxidant. It demonstrated high efficiency in transforming lignin model compounds containing the units and functional groups found in native lignins. The aromatic ring substituents strongly influenced the selectivity of β-ether phenolic dimer cleavage to generate sinapaldehyde and coniferaldehyde, monomers not usually produced by oxidative methods. Time-course studies on two key intermediates provided insight into the reaction pathway. Finally, owing to the broad scope of this oxidation system and the insight gleaned with regard to its mechanism, this strategy could be adapted and applied in a general sense to the production of useful aromatic chemicals from phenolics and lignin.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Durable, High-Performance Unitized Reversible Fuel Cells Based on Proton Conductors
The main objective of this project was to develop robust, highly efficient, and economically viable H + -conducting membrane-based, unitized reversible fuel cell (H-URFC) technology for large-scale co-located energy storage and power generation. Another objective of this project is to gain a profound understanding of the degradation mechanisms of key stack materials and interfaces using various in situ, ex situ, and operando measurements guided by theoretical analysis. Nanostructured components will be integrated into cell design and the interfaces between electrodes and electrolyte will be modified with active bi-functional catalysts and protective coatings in order to achieve >70% roundtrip efficiency at 1 A/cm2 in both the fuel cell and the electrolysis modes. The end goal of the project is to advance the technology to the point that a university-industry collaboration can be established to scale up the technology for early adoption, and eventually enabling a pathway to large-scale energy storage that utilizes chemical storage and conversion for electrical grid balancing.
08 HYDROGEN↗
Enhancement of photocatalytic properties of Bi{sub 2}WO{sub 6} nanoparticles by Pt deposition
Graphical abstract: - Highlights: • Pt/Bi{sub 2}WO{sub 6} was used for photocatalytic degradation of methyl orange dye. • Photocatalytic degradation was dependent on wt% of Pt reaction time, and weight of catalyst. • Kinetic study revealed that the photocatalytic degradation of methyl orange dye followed the first order. • Catalyst re-use revealed the present photocatalyst remain effective and active after five cycles. - Abstract: Bi{sub 2}WO{sub 6} nanoparticles were prepared using a hydrothermal method, and Pt was immobilized on the surface of Bi{sub 2}WO{sub 6} via a photo-assisted deposition (PAD) method. The samples produced were characterized using X-ray diffraction, ultraviolet and visible spectroscopy, photoluminescence emission spectra, transmission electron microscopy, extended X-ray absorption fine structure, and surface area measurements. Furthermore, the catalytic performance of the Bi{sub 2}WO{sub 6} and Pt/Bi{sub 2}WO{sub 6} samples was examined in the degradation of methyl orange dye (MO) under visible light. The extended X-ray absorption fine structure (EXAFS) results, which showed the presence of peaks assigned to the Pt–Pt at approximately 2.50 Å, indicate the formation of nanoscale Pt features. The UV–vis spectral analysis detected a red shift after loading the Pt into the Bi{sub 2}WO{sub 6}. The maximum degradation efficiency achieved was 100% with 0.3 Pt/Bi{sub 2}WO{sub 6} as the photocatalyst after a 30-min reaction time. The catalyst could be reused without any loss in activity for the first five cycles.
36 MATERIALS SCIENCE↗
Realizing efficient operations of Ni-cermet-based fuel cells on hydrocarbons via an in situ self-assembled metal/oxide nano-heterostructured catalyst
Operating Ni-cermet-based fuel cells on hydrocarbons is charming by largely hindered by poor coking tolerance and severe deterioration. Here, in this study, we report an effective metal/oxide nano-heterostructured catalyst with a nominal composition of Pr 0.95 Ru 0.05 O 2-δ (PRO), which is in situ self-assembled to a Pr 0.95 Ru 0.05-x O 2-δ oxide frame coated with Ru metallic nanoparticles (denoted as Ru/PRO) under the operation condition. When applied to the Ni-cermet (Ni-YSZ) anodes, the cells achieve decent peak power densities of 1.784 and 1.870 W cm -2 on CH 4 and C 3 H 8 with only 3% H 2 O at 750 °C, respectively. Moreover, the cells with Ru/PRO-coated anode demonstrate excellent durability when operated on CH 4 for ~ 220 h and C 3 H 8 for ~115 h. It is demonstrated that the Ru/PRO generates hydroxyl species that react with carbon species, followed by the formation of COH intermediates on Ni anode surfaces for removing the coking, as confirmed by experiments and computations.
30 DIRECT ENERGY CONVERSION↗
A Self‐Healing System for Polydicyclopentadiene Thermosets
Self-healing offers promise for addressing structural failures, increasing lifespan, and improving durability in polymeric materials. Implementing self-healing in thermoset polymers faces significant manufacturing challenges, especially due to the elevated temperature requirements of thermoset processing. To introduce self-healing into structural thermosets, the self-healing system must be thermally stable and compatible with the thermoset chemistry. This article demonstrates a self-healing microcapsule-based system stable to frontal polymerization (FP), a rapid and energy-efficient manufacturing process with a self-propagating exothermic reaction (≈200 °C). A thermally latent Grubbs-type complex bearing two N-heterocyclic carbene ligands addresses limitations in conventional G2-based self-healing approaches. Under FP's elevated temperatures, the catalyst remains dormant until activated by a Cu(I) co-reagent, ensuring efficient polymerization of the dicyclopentadiene (DCPD) upon damage to the polyDCPD matrix. The two-part microcapsule system consists of one capsule containing the thermally latent Grubbs-type catalyst dissolved in the solvent, and another capsule containing a Cu(I) coagent blended with liquid DCPD monomer. Using the same chemistry for both matrix fabrication and healing results in strong interfaces as demonstrated by lap-shear tests. In an optimized system, the self-healing system restores the mechanical properties of the tough polyDCPD thermoset. Self-healing efficiencies greater than 90% via tapered double cantilever beam tests are observed.
36 MATERIALS SCIENCE↗
A Broad-Spectrum Catalyst for Aliphatic Polymer Breakdown
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Gao, Jiaxin [Department of Chemistry; University o↗
SO 2 -Induced Selectivity Change in CO 2 Electroreduction
Electrochemical conversion of carbon dioxide (CO 2 ) to value-added chemicals has attracted much attention in recent years as a potential alternative to fossil resources. Although significant works have studied the influence of impurities in the electrolyte (e.g. metal ions), few studies have been performed to understand the influence of gaseous impurities in CO 2 electroreduction. Herein, we study the effects of sulfur dioxide (SO 2 ) on Ag-, Sn-, and Cu-catalyzed CO 2 electrolysis in a flow-cell electrolyzer in near-neutral electrolyte, representing a broad range of CO 2 reduction catalysts. We show that the presence of SO 2 impurity reduces the efficiency of converting CO 2 due to the preferential reduction of SO 2 . In the case of Ag and Sn, the effect of SO 2 impurity was reversible and the catalytic activities of both catalysts were recovered. On the contrary, a shift in selectivity toward formate accompanied with a suppression of multi-carbon (C 2+ ) products was observed on Cu catalyst, demonstrating that Cu is highly sensitive to SO 2 impurity. Furthermore, our results suggest that CO 2 obtained from direct air capture technologies or biorefineries could be more suitable for Cu-catalyzed CO 2 electrolysis as these CO 2 sources would be relatively cleaner (SO 2 -free) than fossil-derived sources such as power plants and can be directly coupled with distributed renewable energy sources such as wind and solar.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Gold Catalysts Synthesized Using a Modified Incipient Wetness Impregnation Method for Propylene Epoxidation
Propylene epoxidation in the presence of oxygen and hydrogen were measured for a series of Au/TS-1 catalysts prepared by a modified incipient wetness impregnation (mIWI) method. This method enables precise control of the Au : Ti ratio in the Au/TS-1 catalysts. The optimized Au/TS-1 catalyst exhibited 12 % propylene conversion, 87 % PO selectivity, and 25 % hydrogen efficiency. The particle size of gold nanoparticles prepared by the modified IWI was between 2 and 3 nm, as demonstrated by XRD patterns, STEM images, and X-ray absorption spectroscopy at the Au L(3)edge. XPS spectra showed that the surface species on the catalysts were similar. UV-Vis spectra suggested that in the modified IWI method, the chlorine ligands in Au(Cl)(4)(-)were replaced by hydroxyl groups, which contributes to form small gold nanoparticles. Kinetic studies showed that the active sites of Au(mIWI)/TS-1 are similar to the Au(DP)/TS-1 prepared by deposition precipitation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Understanding the Active Site Structures and Achieving Catalytic Activity Tuning of Atomically Dispersed FeN 4 Sites for Oxygen Reduction Reaction
Atomically dispersed Fe–—N—C catalysts with high oxygen reduction reaction (ORR) activity have attracted great attention since the last decade. Due to comparable ORR activity and low material cost, they are promising platinum group metal (PGM)-free catalysts that can replace the commercialized Pt/C materials; furthermore, it can facilitate the efficiency of the fuel cell technologies and mitigate dependence on fossil fuels. Great advancements have been made to experimentally optimize the synthesis approach of the Fe–—N—C catalysts, enhance the ORR activity, and improve the catalyst stability. Similarly, recent theoretical studies also provide enriched understanding of the active site structures, properties, and reaction mechanisms. In this review, discussions are made upon utilizing combined experimental and computational spectroscopy to reveal the active site structures, employing mechanistic studies to investigate reaction thermodynamics and kinetics, as well as developing scaling relationships to assist the design and development of future PGM-free catalyst materials. Furthermore, recent advances in studying Fe–—N—C catalysts utilizing electrified surface models and explicit solvation models are also discussed. Not only can these aspects improve the accuracy of theoretical simulation and predictions but also deepen the understanding of the catalyst properties and reaction mechanisms under the effect of surface charges and solvent molecules.
Fe single-atom catalysts↗
In Situ EXAFS Study of Mo–P Bond Dynamics in Molybdenum Phosphide during CO 2 Reduction and Hydrogen Evolution
Transition Metal Phosphides (TMPs) are widely studied as catalysts in reactions like hydrogen evolution, oxygen reduction, and hydrodesulfurization. TMPs have demonstrated remarkable efficiency in accelerating reactions by providing active sites for adsorption and facilitating the transformation of reaction intermediates, a feature that has increased the interest of TMPs in the electrochemical carbon dioxide reduction reaction (eCO 2 RR). Despite their growing use, the potential-dependent structural behavior of TMPs under operating electrochemical conditions remains insufficiently understood. This work investigates the dynamics of the Mo−P bond during eCO 2 RR and hydrogen evolution reaction (HER) using in situ extended X-ray absorption spectroscopy (EXAFS) studies at the Mo−K edge. Structural characterization of the synthesized MoP nanoparticles was performed by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results of the overall electrochemical activity of MoP are presented through linear sweep voltammetry (LSV) experiments in the potential range of 0 to −1.5 V versus Ag/AgCl and chronoamperometry (CA). Liquid products were analyzed by 1 H NMR spectroscopy. The synthesized catalyst showed increasing activity with the highest Faradaic efficiency of 11.75% for C 2+ products at −1.3 V vs Ag/AgCl. In situ EXAFS revealed a change in the average Mo−P bond distance during eCO 2 RR, whereas no such change was observed during the hydrogen evolution reaction (HER). This finding suggests that phosphorus, particularly through modulation of the Mo−P bond length, plays an important role in the eCO 2 RR and demonstrates how in situ EXAFS can track local structural perturbations in MoP catalysts during electrochemical operation, providing complementary structural insight that correlates with electrochemical behavior.
Catalysts↗