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Results for “Electrochemical hydrogenation”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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DOE OSTI2022

Mechanistic Differences between Electrochemical Hydrogenation and Hydrogenolysis of 5‐Hydroxymethylfurfural and Their pH Dependence

Abstract Hydrogenation and hydrogenolysis are two important reactions for electrochemical reductive valorization of biomass‐derived oxygenates such as 5‐hydroxymethylfurfural (HMF). In general, hydrogenolysis (which combines hydrogenation and deoxygenation) is more challenging than hydrogenation (which does not involve the cleavage of carbon–oxygen bonds). Thus, identifying factors and conditions that can promote hydrogenolysis is of great interest for reductive valorization of biomass‐derived oxygenates. For the electrochemical reduction of HMF and its derivatives, it is known that aldehyde hydrogenation is not a part of aldehyde hydrogenolysis but rather a competing reaction; however, no atomic‐level understanding is currently available to explain their electrochemical mechanistic differences. In this study, combined experimental and computational investigations were performed using Cu electrodes to elucidate the key mechanistic differences between electrochemical hydrogenation and hydrogenolysis of HMF. The results revealed that hydrogenation and hydrogenolysis of HMF involve the formation of different surface‐adsorbed intermediates via different reduction mechanisms and that lowering the pH promoted the formation of the intermediates required for aldehyde and alcohol hydrogenolysis. This study for the first time explains the origins of the experimentally observed pH‐dependent selectivities for hydrogenation and hydrogenolysis and offers a new mechanistic foundation upon which rational strategies to control electrochemical hydrogenation and hydrogenolysis can be developed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Electrochemical hydrogen isotope exchange of amines controlled by alternating current frequency

Here, we report an electrochemical protocol for hydrogen isotope exchange (HIE) at α-C(sp 3 )–H amine sites. Tetrahydroisoquinoline and pyrrolidine are selected as two model substrates because of their different proton transfer (PT) and hydrogen atom transfer (HAT) kinetics at the α-C(sp 3 )–H amine sites, which are utilized to control the HIE reaction outcome at different applied alternating current (AC) frequencies. We found the highest deuterium incorporation for tetrahydroisoquinolines at 0 Hz (i.e., under direct current (DC) electrolysis conditions) and pyrrolidines at 0.5 Hz. Analysis of the product distribution and D isotope incorporation at different frequencies reveals that the HIE of tetrahydroisoquinolines is limited by its slow HAT, whereas the HIE of pyrrolidines is limited by the overoxidation of its α-amino radical intermediates. Here, the AC-frequency-dependent HIE of amines can be potentially used to achieve selective labeling of α-amine sites in one drug molecule, which will significantly impact the pharmaceutical industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Unlocking the potential: machine learning applications in electrocatalyst design for electrochemical hydrogen energy transformation

Machine learning (ML) is rapidly emerging as a pivotal tool in the hydrogen energy industry for the creation and optimization of electrocatalysts, which enhance key electrochemical reactions like the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER), the hydrogen oxidation reaction (HOR), and the oxygen reduction reaction (ORR). This comprehensive review demonstrates how cutting-edge ML techniques are being leveraged in electrocatalyst design to overcome the time-consuming limitations of traditional approaches. ML methods, using experimental data from high-throughput experiments and computational data from simulations such as density functional theory (DFT), readily identify complex correlations between electrocatalyst performance and key material descriptors. Leveraging its unparalleled speed and accuracy, ML has facilitated the discovery of novel candidates and the improvement of known products through its pattern recognition capabilities. This review aims to provide a tailored breakdown of ML applications in a format that is readily accessible to materials scientists. Hence, we comprehensively organize ML-driven research by commonly studied material types for different electrochemical reactions to illustrate how ML adeptly navigates the complex landscape of descriptors for these scenarios. We further highlight ML's critical role in the future discovery and development of electrocatalysts for hydrogen energy transformation. Potential challenges and gaps to fill within this focused domain are also discussed. As a practical guide, we hope this work will bridge the gap between communities and encourage novel paradigms in electrocatalysis research, aiming for more effective and sustainable energy solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Electrochemical Hydrogenation of CO on Cu(100): Insights from Accurate Multiconfigurational Wavefunction Methods

Copper (Cu) remains the most efficacious electrocatalyst for electrochemical CO 2 reduction (CO 2 R). Its activity and selectivity are highly facet-dependent. We recently examined the commonly proposed rate-limiting CO hydrogenation step on Cu(111) via embedded correlated wavefunction (ECW) theory and demonstrated that only this higher-level theory yields predictions consistent with potential-dependent experimental kinetics. Here, to understand the differing activities of Cu(111) and Cu(100) in catalyzing CO 2 R, we explore CO hydrogenation on Cu(100) using ECW theory. We predict that the preferred pathway involves the reduction of adsorbed CO (*CO) to *COH via proton-coupled electron transfer (PCET) at working potentials, although *CHO also may form with a kinetically accessible but higher barrier. In contrast, our earlier work on Cu(111) concluded that *COH and *CHO formation via PCET are equally feasible. Furthermore, this work illustrates one possible origin of the facet dependence of CO 2 R mechanisms and products on Cu electrodes and sheds light on how the selectivity of CO 2 R electrocatalysts can be controlled by the surface morphology.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

Synthesis of amorphous Pd-based nanocatalysts for efficient alcoholysis of styrene oxide and electrochemical hydrogen evolution

Amorphous nanomaterials with long-range disordered structures could possess distinct properties and promising applications, especially in catalysis, as compared with their conventional crystalline counterparts. It is imperative to achieve the controlled preparation of amorphous noble metal-based nanomaterials for the exploration of their phase-dependent applications. Here, in this work, we report a facile wet-chemical reduction strategy to synthesize various amorphous multimetallic Pd-based nanomaterials, including PdRu, PdRh, and PdRuRh. The phase-dependent catalytic performances of distinct Pd-based nanomaterials towards diverse catalytic applications have been demonstrated. Specifically, the usage of PdRu nanocatalysts with amorphous and crystalline face-centered cubic (fcc) phases can efficiently switch the ring-opening route of styrene oxide to obtain different products with high selectivity through alcoholysis reaction and hydrogenation reaction, respectively. Moreover, when used as an electrocatalyst for hydrogen evolution reaction (HER), the synthesized amorphous PdRh nanocatalyst exhibits low overpotential and high turnover frequency values, outperforming its crystalline fcc counterpart and most of the reported Pd-based HER electrocatalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Electrochemical hydrogen isotope fractionation - fundamental insights leading to process scale up

Introduction Deuterium and tritium, the two isotopes of hydrogen besides protium, are utilized in many industries. Deuterium is routinely used as a nuclear reactor moderator and molecular labeling agent, while tritium is used as an autoradiography label in medical imaging, and in an emerging market for self-powered lighting for watches, exit signs, firearm night-sights and future fusion fuel. Tritium is produced naturally at very low steady-state levels due to cosmic rays, natural nuclear decay reactions, as well as commercial nuclear fission reactors, and terrestrial nuclear testing conducted primarily in the mid-twentieth century. Tritium often accumulates in the heavy water used in nuclear fission reactors and sometimes appears in groundwater near nuclear reactors due to slight leakage from water sources in the reactor. Because of the health and environmental impacts from tritium leaking into the water sources, as well as the value of this precious material, it is desirable to remove and recover as much tritium as reasonably possible from contaminated water.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Heat recovery from an electrochemical hydrogen separation system

An EHS system includes a EHS cell having an anode, a cathode, and a cooling plate disposed proximate at least one of the anode or the cathode, the cooling plate configured to receive water and configured to output steam or a mixture of water and steam. The system further includes a liquid-vapor separator (LVS) configured to receive the steam or the mixture of water and steam from the cooling plate and to separate water and steam. The LVS is configured to output water to the cooling plate.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2025

Diastereoselectivity Controlled by the Hydrogenation Mechanisms during the Electrochemical Reduction of a Carbonyl Group

Stereocontrol is of critical importance in organic synthesis. In this study, we demonstrate how heterogeneous electrochemical hydrogenation enables diastereocontrol simply by tuning electrochemical hydrogenation mechanisms without altering the adsorption conformation of a reactant on the electrode. We use 4-hydroxy-1-tetralone (4-OH-tetralone) as a model reactant, where diastereomers can be produced during the hydrogenation of the carbonyl group. In traditional thermocatalytic hydrogenation, H 2 first dissociates on the catalyst surface to form surface-adsorbed hydrogen (H*), and therefore, H* is always added to the organic reactant from the catalyst side via hydrogen atom transfer (HAT). Thus, in order to flip the diastereoselectivity, the adsorbed reactant itself must be physically flipped. In contrast, electrochemical hydrogenation can occur either via HAT, where H is added from the electrode surface, or via proton-coupled electron transfer (PCET), where H is added from the solution side of the adsorbed reactant. Thus, without changing the adsorption conformation of the reactant, opposite diastereomers can be obtained by switching the hydrogenation mechanism (HAT vs PCET). In this work, using a combination of experimental and computational studies, we demonstrate two examples of flipping diastereoselectivity by different electrochemical hydrogenation mechanisms. In the first case, we achieve opposite diastereoselectivities using metals that adopt different hydrogenation mechanisms (HAT vs PCET). In the second case, we flip the diastereoselectivity by varying the applied potential, which switches one hydrogenation mechanism to the other on the same metal electrode. In each case, our results offer an atomic-level understanding of the preferred hydrogenation mechanism that enables the corresponding diastereoselectivity.

adsorption↗
DOE OSTI2019

Structural, Electrochemical and Hydrogen Sorption Studies of Nanocrystalline Ti-V-Co and Ti-V-Ni-Co Alloys Synthesized by Mechanical Alloying Method

In this paper, Ti-V-Co and Ti-V-Ni-Co alloys are considered as the hydrogen storage systems and the negative electrodes in Ni-MH{sub x} secondary batteries. This work shows results of studies that have been made on Ti{sub 0.5}V{sub 1.5−x}Co{sub x} and Ti{sub 0.5}V{sub 1.4−x}Ni{sub 0.1}Co{sub x} nanocrystalline alloys (x = 0, 0.1 0.2, 0.3) synthesized by the mechanical alloying technique. The goal of this study is to determine an effect of partial replacement of V by Co atoms on hydrogen storage and electrochemical properties of Ti-V and Ti-V-Ni alloys. X-ray diffraction studies have proven that 14 h of the ball milling has resulted in crystallization of body-centered-cubic solid solution. Studies performed on high-resolution transmission electron microscope confirm creation of nanocrystalline materials. Hydrogen sorption/desorption measurements that have been performed at 303 K show that Co accelerates the hydrogen sorption process, diminishes hysteresis and ameliorates the hydrogen storage reversibility. Properties of Ti-V-Co alloys, described in this work, originate mainly from structure of these materials. Electrochemical measurements of Ti-V-Co alloys have shown these materials poorly absorb hydrogen in 6 M KOH solution. Ti{sub 0.5}V{sub 1.4−x}Ni{sub 0.1}Co{sub x} alloys are characterized by better activation properties and improved cyclability in comparison to Co-free Ti{sub 0.5}V{sub 1.4}Ni{sub 0.1} alloy.

36 MATERIALS SCIENCE↗