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At least 289 records · Page 16

Bismuthene for highly efficient carbon dioxide electroreduction reaction

Bismuth (Bi) has been known as a highly efficient electrocatalyst for CO 2 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 CO 2 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.

Science & Technology - Other Topics↗

Human protein synthesis requires aminoacyl-tRNA pivoting during proofreading

Abstract Rigorous studies have characterized the aa-tRNA selection mechanism in bacteria, which is essential for maintaining translational fidelity. Recent investigations have identified critical distinctions in humans, such as the requirement of subunit rolling and a tenfold slower proofreading step. Although these studies captured key intermediates involved in tRNA selection, they did not elucidate the transitions of aa-tRNA between intermediates. Through diverse structure-based simulations, we simulated 1856 aa-tRNA accommodation events into the human ribosomal A site. Here we show the requirement for a distinct ~30° pivoting of aa-tRNA about the anticodon stem within the accommodation corridor. This pivoting is crucial for navigating the crowded accommodation corridor, which becomes more constrained due to subunit rolling. Subunit rolling-dependent crowding increases the steric contributions of the accommodation corridor during aa-tRNA accommodation, consistent with the tenfold reduction in the rate of proofreading. Furthermore, we show that eEF1A interacts with the accommodating aa-tRNA through conserved basic residues, limiting premature aa-tRNA dissociation from the A site. These findings provide a structural description of the human aa-tRNA selection process and demonstrate that the aa-tRNA alignment relative to the ribosomal catalytic sites is a critical determinant of translational fidelity.

Science & Technology - Other Topics↗

Defective Sn-Zn perovskites through bio-directed routes for modulating CO 2 RR

Sn and Zn oxides can catalyze electrochemical CO 2 reduction reactions (CO 2 RR) to produce useful chemicals. Herein, we report on perovskite-type tin-zinc oxides (TZO) synthesized by a biomineralization approach under benign aqueous conditions. The resulting TZO catalysts are disordered and possess a high quantity of defects, which serve as highly reactive active sites in CO 2 RR. Selectively toward formate or CO is tunable toward the relative amounts of Sn and Zn and their associated O defects. In-situ X-ray absorption spectroscopy measurements reveal electronic and structural transformations consistent with oxygen vacancy formation at Sn-O-Zn bridges as a function of cathodic potential that strongly correlates to CO2RR selectivity. Further, Density functional theory (DFT) calculations demonstrate that introducing an oxygen vacancy in TZO influences drastically influences formate/CO selectivity, consistent with our in-situ XAS findings and catalytic performance. Overall, these findings demonstrate the potential of biomineralization to fabricate perovskite-type metal oxides for energy conversion reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multiple Mechanisms Mapped in Aryl Alkyl Ether Cleavage via Aqueous Electrocatalytic Hydrogenation over Skeletal Nickel

We present here detailed mechanistic studies of electrocatalytic hydrogenation (ECH) in aqueous solution over skeletal nickel cathodes to probe the various paths of reductive catalytic C–O bond cleavage among functionalized aryl ethers relevant to energy science. Heterogeneous catalytic hydrogenolysis of aryl ethers is important both in hydrodeoxygenation of fossil fuels and in upgrading of lignin from biomass. The presence or absence of simple functionalities such as carbonyl, hydroxyl, methyl, or methoxyl groups is known to cause dramatic shifts in reactivity and cleavage selectivity between sp3 C–O and sp2 C–O bonds. Specifically, reported hydrogenolysis studies with Ni and other catalysts have hinted at different cleavage mechanisms for the C–O ether bonds in α-keto and α-hydroxy β-O-4 type aryl ether linkages of lignin. Our new rate, selectivity, and isotopic labeling results from ECH reactions confirm that these aryl ethers undergo C–O cleavage via distinct paths. For the simple 2-phenoxy-1-phenylethane or its alcohol congener, 2-phenoxy-1-phenylethanol, the benzylic site is activated via Ni C–H insertion, followed by beta elimination of the phenoxide leaving group. But in the case of the ketone, 2-phenoxyacetophenone, the polarized carbonyl π system apparently binds directly with the electron rich Ni cathode surface without breaking the aromaticity of the neighboring phenyl ring, leading to rapid cleavage. Substituent steric and electronic perturbations across a broad range of β-O-4 type ethers create a hierarchy of cleavage rates that supports these mechanistic ideas while offering guidance to allow rational design of the catalytic method. Furthermore, on the basis of the new insights, the usage of cosolvent acetone is shown to enable control of product selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Control of Effluent Gases from Solid Waste Processing Using Carbon Nanotubes

One of the major problems associated with solid waste processing technologies is the release of effluent gases and contaminants that are in gaseous formed from the processes. A number of other gases, in particular NO(x), SO2, NH3, Hydrocarbons (e.g. CH4) do present hazards to the crew in space habitats. Reduction of mass, power, volume and resupply can be achieved by using catalyst impregnated carbon nanotubes as compared to other catalytic systems. The development and characterization of an innovative approach for the control and elimination of gaseous toxins using single walled carbon nanotubes (SWNTs) promise superior performance over conventional approaches. This is due to the ability to direct the selective uptake of gaseous species based on their controllable pore size, high adsorptive capacity and the effectiveness of carbon nanotubes as catalyst supports for gaseous conversion. For example, SWNTs have high adsorptive capacity for NO and the adsorbed NO can be decomposed to N2 and O2 . Experimental results showing the decomposition of NO on metal impregnated carbon nanotubes is presented. Equivalent System Mass (ESM) comparisons are made of the existing TCCS systems with the carbon nanotube technology for removing NO(x). The potential for methane decomposition using carbon nanotubes catalysts is also discussed.

Fisher, John↗

Thermal Hydroquinone Oxidation on Co/N-doped Carbon Proceeds by a Band-Mediated Electrochemical Mechanism

Molecules catalyze aerobic oxidation reactions via redox cycling at the metal center to effect sequential activation of O 2 and the substrate. Metal surfaces can catalyze the same transformations by coupling independent half-reactions for oxygen reduction and substrate oxidation mediated via the exchange of band-electrons. Metal/nitrogen-doped carbons (MNCs) are promising catalysts for aerobic oxidation that consist of molecule-like active sites embedded in a conductive carbon host. Owing to their combining molecular and metallic features, it remains unclear whether they proceed via the sequential redox cycling pathways of molecules or the band-mediated pathways of metals. Herein, we simultaneously track the potential of the catalyst and the rate of the turnover of aerobic hydroquinone oxidation on a cobalt-based MNC catalyst contacted to a catalytically inactive carbon electrode. By comparing operando measurements of rate and potential with the current-voltage behavior of each constituent half-reaction under identical conditions, we show that these molecular materials can display the band-mediated reaction mechanisms of extended metallic solids. Further, we show that the action of these band-mediated mechanisms explains fractional reaction orders in both oxygen and hydroquinone, the time evolution of catalyst potential and rate, and the dependence of rate on overall reaction free energy. Selective poisoning experiments suggest that oxygen reduction proceeds at cobalt sites, whereas quinone oxidation proceeds at native oxidic defects on the carbon. These findings highlight that molecule-like active sites can take advantage of band-mediated mechanisms when coupled to conductive hosts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Prediction of Highly Selective Electrocatalytic Nitrogen Reduction at Low Overpotential on a Mo-Doped g-GaN Monolayer

Identifying efficient electrocatalysts with low overpotential and high selectivity for producing ammonia from nitrogen gas is essential for any future electrocatalytic nitrogen reduction reaction (NRR)-based ammonia synthesis. Via density functional theory calculations and the computational hydrogen electrode model, we systematically examine the prospect of using a single-transition-metal (TM)-atom-doped graphene-like GaN (g-GaN) monolayer as an electrocatalyst for artificial nitrogen reduction. Among 15 TMs investigated, the Mo-doped g-GaN (Mo@g-GaN) monolayer is the only electrocatalyst predicted to be feasible for the NRR. The Mo@g-GaN monolayer satisfies all screening criteria considered for activating the inert N≡N triple bond effectively, including stabilization of the adsorbed (*) NRR intermediate *NNH and destabilization of the *NH 2 species. This monolayer also possesses sufficient overall stability. A complete analysis of the likely mechanisms involved in the NRR on this catalyst suggests that the Mo@g-GaN monolayer could exhibit promising NRR catalytic activity. It achieves this via one specific (distal) pathway, which has a very low onset potential of –0.33 V vs the reversible hydrogen electrode (RHE), corresponding to a low overpotential of 0.42 V vs the RHE, defined using the measured equilibrium potential for NRR of 0.09 V vs the RHE. The potential-determining step, conversion of *NH 2 to *NH 3 , also exhibits a surmountable barrier of 0.42 eV, suggesting kinetics will be facile. Finally, the Mo@g-GaN monolayer is predicted to exhibit substantial selectivity (~31%) toward ammonia synthesis over the competing hydrogen evolution reaction. The finding presented in this work may open a potential route for artificial ammonia synthesis using a single-atom catalyst under ambient conditions.

25 ENERGY STORAGE↗

Investigation of NO(x) Removal from Small Engine Exhaust

Contribution of emissions from small engines to the air pollution is significant. Due to differences in operating conditions and economics, the pollution control systems designed for automobiles will be neither suitable nor economically feasible for use on small engines. The objective of this project was to find a catalyst for the removal of NOx from the exhaust of small engines which use a rich air to fuel ratio. The desired catalyst should be inexpensive so that the cost of the pollution control unit will be only a small fraction of the total equipment cost. The high cost of noble metals makes them too expensive for use as NOx catalyst for small engines. Catalytic reduction of NO can also be accomplished by base-metal oxide catalysts. The main disadvantage of base-metal catalysts is their deactivation by poisons and high temperatures. Requirements for the length of the life of the small engine exhaust catalysts are much less than those for automobile exhaust catalysts. Since there is no oxygen in the exhaust gases, reduction selectivity is not a problem. Also, the reducing exhaust gases might help prevent the harmful interactions of the catalyst with the support. For these reasons only the supported metal oxide catalysts were investigated in this project.

Akyurtlu, Ates↗

Dissecting Critical Factors for Electrochemical CO 2 Reduction on Atomically Precise Au Nanoclusters

Here, this work investigates the critical factors impacting electrochemical CO 2 reduction reaction (CO 2 RR) using atomically precise Au nanoclusters (NCs) as electrocatalysts. First, the influence of size on CO 2 RR is studied by precisely controlling NC size in the 1–2.5 nm regime. We find that the electrocatalytic CO partial current density increases for smaller NCs, but the CO Faradaic efficiency (FE) is not directly associated with the NC size. This indicates that the surface-to-volume ratio, i.e. the population of active sites, is the dominant factor for determining the catalytic activity, but the selectivity is not directly impacted by size. Second, we compare the CO 2 RR performance of Au 38 isomers (Au 38 Q and Au 38 T) to reveal that structural rearrangement of identical size NCs can lead to significant changes in both CO 2 RR activity and selectivity. Au 38 Q shows higher activity and selectivity towards CO than Au 38 T, and density functional theory (DFT) calculations reveal that the average formation energy of the key *COOH intermediate on the proposed active sites is significantly lower on Au 38 Q than Au 38 T. These results demonstrate how the structural isomerism can impact stabilization of reaction intermediates as well as the overall CO 2 RR performance of identical size Au NCs. Overall, this work provides important structure–property relationships for tailoring the NCs for CO 2 RR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deciphering Distinct Overpotential-Dependent Pathways for Electrochemical CO 2 Reduction Catalyzed by an Iron–Terpyridine Complex

[Fe(tpyPY2Me)] 2+ ([Fe] 2+ ) is a homogeneous electrocatalyst for converting CO 2 into CO featuring low overpotentials of <100 mV, near-unity selectivity, and high activity with turnover frequencies faster than 100 000 s -1 . To identify the origins of its exceptional performance and inform future catalyst design, we report a combined computational and experimental study that establishes two distinct mechanistic pathways for electrochemical CO 2 reduction catalyzed by [Fe] 2+ as a function of applied overpotential. Electrochemical data shows the formation of two catalytic regimes at low (η TOF/2 of 160 mV) and high (η TOF/2 of 590 mV) overpotential plateaus. We propose that at low overpotentials [Fe] 2+ undergoes a two-electron reduction, two-proton-transfer mechanism (electrochemical-electrochemical-chemical-chemical, EECC), where turnover occurs through the dicationic iron complex, [Fe] 2+ . Computational analysis supports the importance of the singlet ground-state electronic structure for CO 2 binding and that the rate-limiting step is the second protonation in this low-overpotential regime. When more negative potentials are applied, an additional electron-transfer event occurs through either a stepwise or proton-coupled electron-transfer (PCET) pathway, enabling catalytic turnover from the monocationic iron complex ([Fe] + ) via an electrochemical-chemical-electrochemical-chemical (ECEC) mechanism. Comparison of experimental kinetic data obtained from variable controlled potential electrolysis (CPE) experiments with direct product detection with calculated rates obtained from the energetic span model supports the PCET pathway as the most likely mechanism. Moreover, we build upon this mechanistic understanding to propose the design of an improved ligand framework that is predicted to stabilize the key transition states identified in our study and explore their electronic structures using an energy decomposition analysis. Finally, taken together, this work highlights the value of synergistic computational/experimental approaches to decipher mechanisms of new electrocatalysts and direct the rational design of improved platforms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring MoS 2 for Small-Molecule Electroreduction: The Role of Metal Doping and Heterostructures

The electrification of chemical transformations central to sustainable fuel production and waste valorization, such as overall water splitting (OWS), hydrogen evolution reaction (HER), and electrochemical reduction of CO 2 (CO 2 R), presents a powerful opportunity to advance carbon-neutral energy technologies. Transition metal dichalcogenides (TMDs), particularly MoS 2 , have emerged as promising electrocatalyst candidates, owing to their abundance, tunable active sites, and defect-rich structures. This review highlights recent progress in leveraging metal doping and heterostructure engineering of MoS 2 to enhance the electrocatalytic activity and selectivity. By compiling insights from experimental studies and density functional theory (DFT) predictions, we examine how defect creation, electronic structure modification, and interface design contribute to improved charge transport and catalytic efficiency. Particular emphasis is placed on rational design principles, synthetic strategies, and operando characterization methods that provide a pathway to understanding and optimizing MoS 2 -based materials. We also discuss the challenges of stability, mechanistic ambiguity, and scaling while outlining opportunities to bridge theory and experiment. Collectively, this review underscores how defect and heterostructure engineering of MoS 2 can accelerate the development of efficient, sustainable electrocatalysts for both fuel generation and waste-to-value generation.

CO2 reduction↗

Investigation of NOx Removal from Small Engine Exhaust

Contribution of emissions from small engines to the air pollution is significant. Due to differences in operating conditions and economics, the pollution control systems designed for automobiles will be neither suitable nor economically feasible for use on small engines. The objective of this project was to find a catalyst for the removal of NOx from the exhaust of small engines which use a rich air to fuel ratio. The desired catalyst should be inexpensive so that the cost of the pollution control unit will be only a small fraction of the total equipment cost. The high cost of noble metals makes them too expensive for use as NOx catalyst for small engines. Catalytic reduction of Nitrogen Oxide (NO) can also be accomplished by base-metal oxide catalysts. The main disadvantage of base-metal catalysts is their deactivation by poisons and high temperatures. Requirements for the length of the life of the small engine exhaust catalysts are much less than those for automobile exhaust catalysts. Since there is no oxygen in the exhaust gases, reduction selectivity is not a problem. Also, the reducing exhaust gases might help prevent the harmful interactions of the catalyst with the support. For these reasons only the supported metal oxide catalysts were investigated in this project.

Akyurtlu, Ates↗

Lignin Extraction and Condensation as a Function of Temperature, Residence Time, and Solvent System in Flow-through Reactors

Solvolytic extraction of lignin from biomass is a critical step in lignin-first biorefining, including the reductive catalytic fractionation (RCF) process. Key to optimal RCF processing is the ability to rapidly extract lignin from biomass at high delignification extents and transfer the lignin molecules to a catalyst surface in a time frame that minimizes lignin condensation reactions. Here, we use a flow-through reactor to study the effects of temperature (175–250 °C), residence time (9 to 36 min), and solvent composition (methanol and methanol–water) on lignin extraction and condensation. We evaluated three metrics at each condition: total delignification, delignification rate, and extent of condensation, the latter measured by a decrease in monomer yield for batch hydrogenolysis reactions of solvolysis liquor compared to batch RCF reactions. We observe that delignification is predominantly determined by temperature, while residence time dictates the lignin condensation extent. Moreover, the extent of both extraction and condensation increased in the methanol–water solvent system compared to that in the methanol system. Lignin extracted in methanol is stable up to 18-min residence times at or below 225 °C, while a majority of the lignin extracted in methanol–water is condensed with a 9-min residence time at 200 °C. These results can inform reactor designs and solvent selection for lignin-first biorefining processes that aim to physically separate the biomass and catalyst.

biorefining↗

Cobalt promotion of the InO x –TiO 2 heterojunction for dual photothermal reduction of CO 2

A series of cobalt-promoted indium–titanium composite oxides was synthesized using a microemulsion method. Their functional properties were investigated for the photothermal reduction of carbon dioxide. In this series, the indium content varied between 2.5 and 20%, while the cobalt percentage was kept constant at 4% throughout the series. In all cases, carbon monoxide formation occurred selectively through the reverse water gas shift reaction. The sample with 2.5% In maximized the synergistic use of the two energy sources, while the sample with 10% In showed the highest catalytic activity under both thermal and dual photo-thermo conditions. A physicochemical characterization was performed for all samples. The use of microscopy and X-ray absorption spectroscopy demonstrated that sub-nanometric indium entities, in combination with atomically dispersed cobalt oxide entities, achieved a balance between high thermal activity and significant synergy between light and heat in a catalytic process. The system with 10% indium is thus able to improve the thermal catalytic process through the use of light, providing an intensification procedure for the classic process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal–Nitrogen–Carbon Cluster–Decorated Titanium Carbide is a Durable and Inexpensive Oxygen Reduction Reaction Electrocatalyst

Clusters of nitrogen- and carbon-coordinated transition metals dispersed in a carbon matrix (e. g., Fe-N-C) have emerged as an inexpensive class of electrocatalysts for the oxygen reduction reaction (ORR). In this work, it was shown that optimizing the interaction between the nitrogen-coordinated transition metal clusters embedded in a more stable and corrosion-resistant carbide matrix yielded an ORR electrocatalyst with enhanced activity and stability compared to Fe-N-C catalysts. Utilizing first-principles calculations, an electrostatics-based descriptor of catalytic activity was identified, and nitrogen-coordinated iron (FeN 4 ) clusters embedded in a TiC matrix were predicted to be an efficient platinum-group metal (PGM)-free ORR electrocatalyst. Guided by theory, selected catalyst formulations were synthesized, and it was demonstrated that the experimentally observed trends in activity fell exactly in line with the descriptor-derived theoretical predictions. The Fe-N-TiC catalyst exhibited enhanced activity (20 %) and durability (3.5-fold improvement) compared to a traditional Fe-N-C catalyst. It was posited that the electrostatics-based descriptor provides a powerful platform for the design of active and stable PGM-free electrocatalysts and heterogenous single-atom catalysts for other electrochemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Au-activated N motifs in non-coherent cupric porphyrin metal organic frameworks for promoting and stabilizing ethylene production

Direct implementation of metal-organic frameworks as the catalyst for CO 2 electroreduction has been challenging due to issues such as poor conductivity, stability, and limited > 2e - products. In this study, Au nanoneedles are impregnated into a cupric porphyrin-based metal-organic framework by exploiting ligand carboxylates as the Au 3+ -reducing agent, simultaneously cleaving the ligand-node linkage. Surprisingly, despite the lack of a coherent structure, the Au-inserted framework affords a superb ethylene selectivity up to 52.5% in Faradaic efficiency, ranking among the best for metal-organic frameworks reported in the literature. Through operando X-ray, infrared spectroscopies and density functional theory calculations, the enhanced ethylene selectivity is attributed to Au-activated nitrogen motifs in coordination with the Cu centers for C-C coupling at the metalloporphyrin sites. Furthermore, the Au-inserted catalyst demonstrates both improved structural and catalytic stability, ascribed to the altered charge conduction path that bypasses the incoherent framework. This study underlines the modulation of reticular metalloporphyrin structure by metal impregnation for steering the CO 2 reduction reaction pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advancing electrocatalytic nitrogen fixation: insights from molecular systems

Nitrogen fixation has a rich history within the inorganic chemistry community. In recent years attention has (re)focused on developing electrocatalytic systems capable of mediating the nitrogen reduction reaction (N 2 RR). Well-defined molecular catalyst systems have much to offer in this context. This personal perspective summarizes recent progress from our laboratory at Caltech, pulling together lessons learned from a number of studies we have conducted, placing them within the broader context of thermodynamic efficiency and selectivity for the N 2 RR. Here, in particular, proton-coupled electron transfer (PCET) provides an attractive strategy to achieve enhanced efficiency for the multi-electron/proton reduction of N 2 to produce NH 3 (or NH 4 + ), and electrocatalytic PCET (ePCET) via an ePCET mediator affords a promising means of mitigating HER such that the N 2 RR can be achieved in a catalytic fashion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-throughput screening to predict highly active dual-atom catalysts for electrocatalytic reduction of nitrate to ammonia

Ammonia is an essential chemical owing to its importance in fertilizer production and other industrial applications. Electrocatalytic nitrate reduction to ammonia (NO 3 RR) holds great promise for low-temperature ammonia production while simultaneously addressing nitrate-based environmental concerns. To provide the mechanistic understanding needed to design an effective electrocatalyst, we systematically investigated the catalytic performance of metal-based dual-atom catalysts (DACs) anchored on two-dimensional (2D) expanded phthalocyanine (Pc) for NO 3 RR. We found that NO 3 RR can efficiently produce ammonia on Cr 2 -Pc, V 2 -Pc, Ti 2 -Pc, and Mn 2 -Pc surfaces with low limiting potentials of – 0.02, – 0.25, – 0.34, and – 0.41 V RHE , respectively. Moreover, using the free energy difference of *NO 3 - and *H as a descriptor, we found that the hydrogen evolution reaction is significantly suppressed on the DAC surface due to an ensemble effect in which the two metal atoms cooperate to selectively form ammonia. We performed high-throughput screening to develop an efficient metal-based DAC for NO 3 - reduction, followed by a mechanistic study to elucidate the NO3RR pathway on the DAC. Finally, this work provides design information for advancing sustainable ammonia synthesis under ambient conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗