Co-catalytic metal–support interactions in single-atom electrocatalysts

Nature Reviews Materials, Journal Year: 2024, Volume and Issue: 9(3), P. 173 - 189

Published: Jan. 10, 2024

Language: Английский

---

Electrocatalytic Reduction of Nitrate to Ammonia via a Au/Cu Single Atom Alloy Catalyst

Environmental Science & Technology, Journal Year: 2023, Volume and Issue: 57(8), P. 3134 - 3144

Published: Feb. 14, 2023

Electrocatalytic ammonia (NH3) synthesis from the reduction of nitrate (NO3-) is one effective and mild methods to treat nitrogen-containing wastewater stationary sources obtain NH3 readily compared with Haber-Bosch process. However, low efficiency electrocatalytic NO3- on traditional Cu-based catalysts hinders their practical application. Here, we prepare a Au/Cu single atom (SA) alloy (Au/Cu SAA) that shows high performance 99.69% Faradaic at -0.80 V vs RHE. The structures Au SAs alloyed are confirmed by detailed characterizations. Online differential electrochemical mass spectrometry confirms occurrence key reaction intermediates (*NO2, *NO, *NH3). Density functional theory calculations demonstrate efficiently reduce adsorption energy *NO3-, newly formed Au-Cu bonds boost process *NO2 *NO. Meanwhile, SAAs produce significantly less N2 N2O byproducts due prohibition N-N coupling atoms, which finally leads excellent selectivity.

Language: Английский

---

Electrocatalytic Refinery of Biomass-Based 5-Hydroxymethylfurfural to Fine Chemicals

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(17), P. 11204 - 11231

Published: Aug. 10, 2023

Because of depleting fossil-fuel reserves, together with the impacts climate change, alternative eco-friendly production high-value chemicals and renewables is needed. Biomass feedstock particular research interest. 5-Hydroxymethylfural (HMF) a versatile precursor that can be converted to via electrolysis. Reduction generates precursors for ethers, ketones, polyurethanes, polyesters, polyethers, e.g., 2,5-dihydroxymethylfuran (DHMF) 2,5-dimethyletrahydrofuran (DHMTHF), high-energy-density premium biofuels, 2,5-dimethylfuran (DMF), 2,5-hexanedione (HD) 5,5′-bis(hydroxymethyl) hydrofuroin (BHH). Oxidation HMF yields valuable chemical products, including 2,5-diformyl furan (DFF), 5-hydroxymethyl-2-furan carboxylic acid (HMFCA), 2,5-furan dicarboxylic (FDCA), maleic (MA) are precursors/intermediates polymer industry chemical/pharmaceutical production(s). In this review, we 1) report comparative summary electrocatalytic refinery HMF, both electro-oxidation electroreduction pathways, 2) appraise advances in reaction (HRR) (HOR), 3) assess pathways mechanisms, 4) establish design electrocatalysts selection metal materials, geometric structure, electronic structural modifications boost HRR HOR activity selectivity, 5) evaluate impact parameters pH, electrolyte composition, applied potential, initial substrate concentration on HOR, 6) provide prospect future electrochemical refinement HMF. We conclude an improved understanding conditions needed practically selectivity Findings will benefit electrochemistry chemistry generating fine and, therefore, interest researchers manufacturers.

Language: Английский

---

Urea Electrosynthesis from Nitrate and CO₂ on Diatomic Alloys

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(30)

Published: June 14, 2024

Abstract Urea electrosynthesis from co–electrolysis of NO 3 − and CO 2 (UENC) offers a promising technology for achieving sustainable efficient urea production. Herein, diatomic alloy catalyst (CuPd 1 Rh –DAA), with mutually isolated Pd atoms alloyed on Cu substrate, is theoretically designed experimentally confirmed to be highly active selective UENC catalyst. Combining theoretical computations operando spectroscopic characterizations reveals the synergistic effect –Cu sites promote via tandem catalysis mechanism, where site triggers early C–N coupling promotes *CO –to–*CO NH steps, while facilitates subsequent protonation step *COOHNH toward formation. Impressively, CuPd –DAA assembled in flow cell presents highest Faradaic efficiency 72.1% yield rate 53.2 mmol h −1 g cat at −0.5 V versus RHE, representing nearly performance among all reported catalysts.

Language: Английский

---

Efficient electrosynthesis of formamide from carbon monoxide and nitrite on a Ru-dispersed Cu nanocluster catalyst

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 19, 2023

Conversion into high-value-added organic nitrogen compounds through electrochemical C-N coupling reactions under ambient conditions is regarded as a sustainable development strategy to achieve carbon neutrality and high-value utilization of harmful substances. Herein, we report an process for selective synthesis high-valued formamide from monoxide nitrite with Ru1Cu single-atom alloy conditions, which achieves high selectivity Faradaic efficiency 45.65 ± 0.76% at -0.5 V vs. RHE. In situ X-ray absorption spectroscopy, coupled in Raman spectroscopy density functional theory calculations results reveal that the adjacent Ru-Cu dual active sites can spontaneously couple *CO *NH2 intermediates realize critical reaction, enabling high-performance electrosynthesis formamide. This work offers insight electrocatalysis CO NO2- paving way more-sustainable chemical products.

Language: Английский

---

Ambient Electrosynthesis toward Single‐Atom Sites for Electrocatalytic Green Hydrogen Cycling

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(14)

Published: Feb. 17, 2023

With the ultimate atomic utilization, well-defined configuration of active sites and unique electronic properties, catalysts with single-atom (SASs) exhibit appealing performance for electrocatalytic green hydrogen generation from water splitting further utilization via hydrogen-oxygen fuel cells, such that a vast majority synthetic strategies toward SAS-based (SASCs) are exploited. In particular, room-temperature electrosynthesis under atmospheric pressure offers novel, safe, effective route to access SASs. Herein, recent progress in ambient SASs sustainable future opportunities discussed. A systematic summary is started on three kinds electrochemically routes SASs, including electrochemical etching (ECE), direct electrodeposition (DED), leaching-redeposition (ELR), associated advanced characterization techniques. Next, their applications energy conversion evolution reaction, oxygen overall splitting, reduction reaction reviewed. Finally, brief conclusion remarks challenges regarding development high-performance cost-effective SASCs many other presented.

Language: Английский

---

Dopant- and Surfactant-Tuned Electrode–Electrolyte Interface Enabling Efficient Alkynol Semi-Hydrogenation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(11), P. 6516 - 6525

Published: March 13, 2023

Electrochemical alkynol semi-hydrogenation has emerged as a sustainable and environmentally benign route for the production of high-value alkenols, featuring water hydrogen source instead H2. It is highly challenging to design electrode-electrolyte interface with efficient electrocatalysts their matched electrolytes break selectivity-activity stereotype. Here, boron-doped Pd catalysts (PdB) surfactant-modified are proposed enable simultaneous increase in alkenol selectivity conversion. Typically, compared pure commercial Pd/C catalysts, PdB catalyst achieves both higher turnover frequency (139.8 h-1) specific (above 90%) 2-methyl-3-butyn-2-ol (MBY). Quaternary ammonium cationic surfactants that employed electrolyte additives assembled at electrified response applied bias potential, establishing an interfacial microenvironment can facilitate transfer hinder suitably. Eventually evolution reaction inhibited promoted, without inducing decrease selectivity. This work offers distinct perspective on creating suitable electrosynthesis.

Language: Английский

---

Metal Alloys‐Structured Electrocatalysts: Metal–Metal Interactions, Coordination Microenvironments, and Structural Property–Reactivity Relationships

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(51)

Published: April 24, 2023

Metal alloys-structured electrocatalysts (MAECs) have made essential contributions to accelerating the practical applications of electrocatalytic devices in renewable energy systems. However, due complex atomic structures, varied electronic states, and abundant supports, precisely decoding metal-metal interactions structure-activity relationships MAECs still confronts great challenges, which is critical direct future engineering optimization MAECs. Here, this timely review comprehensively summarizes latest advances creating MAECs, including interactions, coordination microenvironments, relationships. First, fundamental classification, design, characterization, structural reconstruction are outlined. Then, merits modulation strategies recent breakthroughs for noble non-noble metal-structured thoroughly discussed, such as solid solution alloys, intermetallic single-atom alloys. Particularly, unique insights into bond theoretical understanding, operando techniques mechanism disclosure given. Thereafter, current states diverse with a focus on property-reactivity relationships, reaction pathways, performance comparisons discussed. Finally, challenges perspectives systematically It believed that comprehensive can offer substantial impact stimulating widespread utilization metal materials electrocatalysis.

Language: Английский

---

Hydrogen spillover as a promising strategy for boosting heterogeneous catalysis and hydrogen storage

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 471, P. 144691 - 144691

Published: July 8, 2023

Language: Английский

---

Electrochemical hydrogenation and oxidation of organic species involving water

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(4), P. 277 - 293

Published: March 25, 2024

Language: Английский

---