Recent advances in nanostructured heterogeneous catalysts for N-cycle electrocatalysis

Deleted Journal, Journal Year: 2022, Volume and Issue: 1, P. e9120010 - e9120010

Published: May 30, 2022

To restore the natural nitrogen cycle (N-cycle), artificial N-cycle electrocatalysis with flexibility, sustainability, and compatibility can convert intermittent renewable energy (e.g., wind) to harmful or value-added chemicals minimal carbon emissions. The background of such N-cycles, as fixation, ammonia oxidation, nitrate reduction, is briefly introduced here. discussion emerging nanostructures in various conversion reactions focused on architecture/compositional design, electrochemical performances, reaction mechanisms, instructive tests. Energy device advancements for achieving more functions well in situ/operando characterizations toward understanding key steps are also highlighted. Furthermore, some recently proposed less discussed C–N coupling summarized. We classify inorganic sources that each other under an applied voltage into three types, namely, abundant nitrogen, toxic (nitrite), oxides, useful compounds ammonia, hydrazine, hydroxylamine, goal providing critical insights strategies facilitate development our circular economy.

Language: Английский

---

Advances in ammonia electrosynthesis from ambient nitrate/nitrite reduction

Chem, Journal Year: 2023, Volume and Issue: 9(7), P. 1768 - 1827

Published: June 21, 2023

Language: Английский

---

Sub-nm RuO_x Clusters on Pd Metallene for Synergistically Enhanced Nitrate Electroreduction to Ammonia

ACS Nano, Journal Year: 2023, Volume and Issue: 17(2), P. 1081 - 1090

Published: Jan. 11, 2023

The electrochemical nitrate reduction to ammonia reaction (NO3RR) has emerged as an appealing route for achieving both wastewater treatment and production. Herein, sub-nm RuOx clusters anchored on a Pd metallene (RuOx/Pd) are reported highly effective NO3RR catalyst, delivering maximum NH3-Faradaic efficiency of 98.6% with corresponding NH3 yield rate 23.5 mg h–1 cm–2 partial current density 296.3 mA at −0.5 V vs RHE. Operando spectroscopic characterizations combined theoretical computations unveil the synergy enhance energetics through mechanism hydrogen spillover hydrogen-bond interactions. In detail, activates NO3– form intermediates, while dissociates H2O generate *H, which spontaneously migrates RuOx/Pd interface via process. Further interactions between spillovered *H intermediates makes desorb from participate in intermediate hydrogenation, contributing enhanced activity NO3–-to-NH3 conversion.

Language: Английский

---

Electrochemical Nitrate Reduction: Ammonia Synthesis and the Beyond

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(17)

Published: June 9, 2023

Natural nitrogen cycle has been severely disrupted by anthropogenic activities. The overuse of N-containing fertilizers induces the increase nitrate level in surface and ground waters, substantial emission oxides causes heavy air pollution. Nitrogen gas, as main component air, used for mass ammonia production over a century, providing enough nutrition agriculture to support world population increase. In last decade, researchers have made great efforts develop processes under ambient conditions combat intensive energy consumption high carbon associated with Haber-Bosch process. Among different techniques, electrochemical reduction reaction (NO

Language: Английский

---

Recent advances in electrocatalytic ammonia synthesis

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2023, Volume and Issue: 50, P. 6 - 44

Published: July 1, 2023

Language: Английский

---

Recent Advances in Electrocatalysts for Efficient Nitrate Reduction to Ammonia

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(43)

Published: June 25, 2023

Abstract Ammonia as an irreplaceable chemical has been widely demanded to keep the sustainable development of modern society. However, its industrial production consumes huge energy and releases extraordinary green‐house gases, leading various environmental issues. To achieve green ammonia is a great challenge that extensively pursued recently. In review, most promising strategy, electrochemical nitrate reduction reaction (e‐NO 3 RR) for purpose comprehensively investigated give full understanding mechanism provide guidance future directions. Particularly, electrocatalysts focused realize high yield rate Faraday efficiency applications. The recent‐developed catalysts, including noble metallic materials, alloys, metal compounds, single‐metal‐atom metal‐free are systematically discussed review effects factors on catalytic performance in e‐NO RR. Accordingly, strategies, defects engineering, coordination environment modulating, surface controlling, hybridization, carefully improve performance, such intrinsic activity selectivity. Finally, perspectives challenges given out. This shall insightful advanced systems efficiently industry.

Language: Английский

---

Governing Interlayer Strain in Bismuth Nanocrystals for Efficient Ammonia Electrosynthesis from Nitrate Reduction

ACS Nano, Journal Year: 2022, Volume and Issue: 16(3), P. 4795 - 4804

Published: March 1, 2022

Electrochemical ammonia (NH3) synthesis from nitrate (NO3-) reduction offers an intriguing approach for both sustainable and environmental denitrification, yet it remains hindered by a complicated reaction pathway with various intermediates. Here we present that the interlayer strain compression in bismuth (Bi) nanocrystals can contribute to activity selectivity improvement toward NH3 electrosynthesis NO3- reduction. By virtue of comprehensive spectroscopic studies theoretical calculations, untangle lattice shortens Bi-Bi bond broaden 6p bandwidth electron delocalization, promoting chemical affinities nitrogen Such manipulation facilitates activation reduce energy barrier improvement, also alleviates *NO2 desorption suppress nitrite generation. As result, strain-compressive Bi electrocatalyst yields maximal Faradaic efficiency 90.6% high generation rate 46.5 g h-1 gcat-1 industrially scalable partial current density up 300 mA cm-2 product at optimized conditions, respectively.

Language: Английский

---

High-Efficiency Electrochemical Nitrate Reduction to Ammonia on a Co₃O₄ Nanoarray Catalyst with Cobalt Vacancies

ACS Applied Materials & Interfaces, Journal Year: 2022, Volume and Issue: 14(41), P. 46595 - 46602

Published: Oct. 5, 2022

Electrocatalytic nitrate reduction reaction (NO3RR) affords a bifunctional character in the carbon-free ammonia synthesis and remission of pollution water. Here, we fabricated Co3O4 nanosheet array with cobalt vacancies on carbon cloth (vCo-Co3O4/CC) by situ etching aluminum-doped Co3O4/CC, which exhibits an excellent Faradaic efficiency 97.2% large NH3 yield as high 517.5 μmol h-1 cm-2, better than pristine Co3O4/CC. Theoretical calculative results imply that can tune local electronic environment around Co sites Co3O4, increasing charge reducing electron cloud density sites, is thus conducive to adsorption NO3- for greatly enhanced reduction. Furthermore, vCo-Co3O4 (311) facet presents NO3RR activity low energy barrier about 0.63 eV potential-determining step, much smaller (1.3 eV).

Language: Английский

---

Recent progress and strategies on the design of catalysts for electrochemical ammonia synthesis from nitrate reduction

Inorganic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(12), P. 3489 - 3514

Published: Jan. 1, 2023

Ammonia (NH3) is an essential raw material in the production of fertilizers and a promising carbon-free energy carrier, however, its synthesis still depends on energy- capital-intensive Haber–Bosch process. Recently, electrochemical N2 reduction reaction has attracted significant interest as emerging method for NH3 under ambient conditions. However, limited solubility aqueous electrolyte strong NN bonds result low yield rate, inferior faradaic efficiency unsatisfactory selectivity, impeding further practical application. Considering high water nitrate (NO3−), NO3− (NO3−RR) become fascinating route achieving sustainable NH3, enormous progress been made this field. As consequence, review discusses mechanism systematically summarizes recent development electrocatalysts NO3−RR, including noble-metal-based materials, single-atom metal catalysts, transition-metal-based catalysts. Diverse design strategies catalysts to boost NO3−RR performance, such defect engineering, rational structure design, strain engineering constructing heterostructures, are discussed. This followed by illustration how robust understanding optimization affords fundamental insights into efficiency, selectivity electrocatalysts. Finally, we conclude with future perspectives critical issues, challenges research directions high-efficiency selective NH3.

Language: Английский

---

Weakened d–p orbital hybridization inin situreconstructed Ru/β-Co(OH)₂heterointerfaces for accelerated ammonia electrosynthesis from nitrates

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(6), P. 2483 - 2493

Published: Jan. 1, 2023

Electron-deficient Ru sites at Ru/Co(OH) 2 heterointerfaces weaken the d–p orbital hybridization ability and further facilitate desorption of ammonia intermediates, thereby achieving ultrahigh nitrate electroreduction activity towards ammonia.

Language: Английский

---