Synthesis of Hydroxylamine via Ketone-Mediated Nitrate Electroreduction

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10934 - 10942

Published: April 6, 2024

Hydroxylamine (HA, NH2OH) is a critical feedstock in the production of various chemicals and materials, its efficient sustainable synthesis great importance. Electroreduction nitrate on Cu-based catalysts has emerged as promising approach for green ammonia (NH3) production, but electrosynthesis HA remains challenging due to overreduction NH3. Herein, we report first work ketone-mediated using water. A metal–organic-framework-derived Cu catalyst was developed catalyze reaction. Cyclopentanone (CP) used capture situ form CP oxime (CP-O) with C═N bonds, which prone hydrolysis. could be released easily after electrolysis, regenerated. It demonstrated that CP-O formed an excellent Faradaic efficiency 47.8%, corresponding formation rate 34.9 mg h–1 cm–2, remarkable carbon selectivity >99.9%. The hydrolysis release regeneration also optimized, resulting 96.1 mmol L–1 stabilized solution, significantly higher than direct reduction. Detailed characterizations, control experiments, theoretical calculations revealed surface reconstruction reaction mechanism, showed coexistence Cu0 Cu+ facilitated protonation reduction *NO2 *NH2OH desorption, leading enhancement production.

Language: Английский

---

Nitrogenous Intermediates in NO_x‐involved Electrocatalytic Reactions

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Jan. 16, 2024

Abstract Chemical manufacturing utilizing renewable sources and energy emerges as a promising path towards sustainability carbon neutrality. The electrocatalytic reactions involving nitrogen oxides (NO x ) offered potential strategy for synthesizing various nitrogenous chemicals. However, it is currently hindered by low selectivity/efficiency limited reaction pathways, mainly due to the difficulties in controllable generation utilization of intermediates. In this minireview, focusing on intermediates NO ‐involved reactions, we discuss newly developed methodologies studying controlling generation, conversion, intermediates, which enable recent developments that yield products, including ammonia (NH 3 ), organonitrogen molecules, compounds exhibiting unconventional oxidation states. Furthermore, also make an outlook highlight future directions emerging field reactions.

Language: Английский

---

Advances in In Situ Investigations of Heterogeneous Catalytic Ammonia Synthesis

Catalysts, Journal Year: 2025, Volume and Issue: 15(2), P. 160 - 160

Published: Feb. 9, 2025

Ammonia is a key “platform” raw chemical for fertilizers and nitrogen-containing chemicals, with global annual production of ~180 million tons. Recently, ammonia has also come to be seen as an excellent hydrogen-containing liquid promising long-term, large-scale hydrogen storage transport. Therefore, artificial N2 fixation, synthesis reaction, will play pivotal role influencing food energy human society. Till now, industrial relied on high temperature pressure (420~500 °C, 10~15 MPa). Researchers are devoted developing new catalysts well optimizing the traditional Fe-based continuously. However, relation between catalysts’ detailed structure efficiency not yet fully understood, which crucial provide guidance further improving efficacy this importance reaction. in situ characterization techniques have achieved significant improvements understandings been central topic catalysis. In review, recent advances investigations heterogeneous catalytic summarized results discussed. end, concluding remark perspective proposed, hope inspiring future dedicated unveiling principles designing synthesis.

Language: Английский

---

Lignin-derived carbon nanosheets boost electrochemical reductive amination of pyruvate to alanine

iScience, Journal Year: 2023, Volume and Issue: 26(10), P. 107776 - 107776

Published: Aug. 29, 2023

Efficient and sustainable amino acid synthesis is essential for industrial applications. Electrocatalytic reductive amination has emerged as a promising method, but challenges such undesired side reactions low efficiency persist. Herein, we demonstrated lignin-derived catalyst alanine synthesis. Carbon nanosheets (CNSs) were synthesized from lignin via template-assisted method doped with nitrogen sulfur to boost suppress reactions. The resulting N,S-co-doped carbon (NS-CNSs) exhibited outstanding electrochemical performance. It achieved maximum Faradaic of 79.5%, yield exceeding 1,199 μmol h-1 cm-2 on NS-CNS, selectivity above 99.9%. NS-CNS showed excellent durability during long-term electrolysis. Kinetic studies including control experiments theoretical calculations provided further insights into the reaction pathway. Moreover, catalysts potential in upgrading real-world polylactic plastic waste, yielding value-added over 75%.

Language: Английский

---

Active hydrogen-controlled CO₂/N₂/NO_x electroreduction:From mechanism understanding to catalyst design

The Innovation Materials, Journal Year: 2024, Volume and Issue: 2(1), P. 100058 - 100058

Published: Jan. 1, 2024

<p>The development of renewable-energy-powered electrocatalysis meets the need for sustainable society. With water as proton source, it enables efficient production chemicals and fuels from renewable resources like CO₂, N₂, NO_x under ambient conditions. Hydrogen generated via dissociation is a crucial participant in transforming reactants into desired products, but also serves direct source undesired reactions when excess. In this review, we first present an overview functional mechanisms active hydrogen electroreduction CO₂/N₂/NO_x. We then introduce range methods to enhance our understanding these mechanisms. Furthermore, detailed discussion design strategies aimed at regulating reduction CO₂/N₂/NO_x provided. Finally, outlook on critical challenges remaining research area promising opportunities future considered.</p>

Language: Английский

---

Femtosecond laser-enabled facile tuning of Cu selectivity towards long-chain products in CO2 electroreduction

Journal of CO2 Utilization, Journal Year: 2024, Volume and Issue: 85, P. 102880 - 102880

Published: July 1, 2024

In the quest to mitigate excessive CO2 emissions, electrochemical reduction of (eCO2R) into multi-carbon fuels and vital chemical precursors emerges as a compelling strategy. Meticulous control C–C coupling on catalyst surface is grand challenge in selective production desired C2+ products. Ethane propanol are among most desirable products gas liquid phase, respectively. Herein, we demonstrate facile femtosecond laser-enabled tuning Cu selectivity towards ethane propanol. The tailoring induces shift from C1 This product composition attributed concurrent creation hierarchical porous structures, stabilization {111}, {200}, {220} Cu2O facets, promotion Cu1+ oxidation state. These alterations collectively enhance adsorption strength, leading an increased propensity for C-C and, consequently, elevated toward

Language: Английский

---

Nitrogenous Intermediates in NO_x‐involved Electrocatalytic Reactions

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(15)

Published: Jan. 16, 2024

Abstract Chemical manufacturing utilizing renewable sources and energy emerges as a promising path towards sustainability carbon neutrality. The electrocatalytic reactions involving nitrogen oxides (NO x ) offered potential strategy for synthesizing various nitrogenous chemicals. However, it is currently hindered by low selectivity/efficiency limited reaction pathways, mainly due to the difficulties in controllable generation utilization of intermediates. In this minireview, focusing on intermediates NO ‐involved reactions, we discuss newly developed methodologies studying controlling generation, conversion, intermediates, which enable recent developments that yield products, including ammonia (NH 3 ), organonitrogen molecules, compounds exhibiting unconventional oxidation states. Furthermore, also make an outlook highlight future directions emerging field reactions.

Language: Английский

---

Zinc Nanoparticles Electrodeposited on TiO₂Nanotube Arrays Using Deep Eutectic Solvents for Implantable Electrochemical Sensors

ACS Applied Nano Materials, Journal Year: 2023, Volume and Issue: 6(10), P. 8238 - 8249

Published: April 17, 2023

This work reports on the electrodeposition of zinc nanoporous metal oxide titania nanotube arrays (TiO2 NTAs) using a zinc-containing deep eutectic solvent (Zn2+–DES). The effects substrate morphology and crystallinity, deposition temperature, concentration, time electrochemical properties Zn/TiO2 NTAs were investigated. Two-dimensional nanohexagons (NHexs) with mean diameter ∼300 nm thickness 10–20 decorated onto TiO2 (with pore ∼80 tube length ∼5 μm) via at −1.6 V Zn2+–DES. Cyclic voltammetry tests Zn2+–DES electrolyte revealed an window ∼3.5 V, diffusion coefficient Zn2+ was found to be 4.29 × 10–10 cm2 s–1 room temperature 7.10 40 °C. Zinc nucleation NTA substrates followed instantaneous model. Using higher increased growth rate NHexs, while annealing improve their uniformity morphology. During initial stage deposition, hexagonal close-packed NHexs preferentially grow tetragonal anatase NTAs. resulted in lowering impedance improving overall developed this study offer promising electrocatalyst material system for implantable sensors.

Language: Английский

---

Engineering uranyl sites into MOFs for efficient and highly selective photocatalytic CO₂ reduction

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(19), P. 6493 - 6501

Published: Jan. 1, 2024

IHEP-101 features uranyl photocatalytic active sites for the efficient photoreduction of CO 2 . By combining in situ DRIFTS and theoretical calculations, mechanism by has been clearly elucidated.

Language: Английский

---

Industrial-Grade Electrocatalytic Synthesis of Glycine from Oxalic Acid and Nitrate Using a Porous PbSnBi Catalyst

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: unknown, P. 124653 - 124653

Published: Sept. 1, 2024

Language: Английский

---