Advances in ammonia electrosynthesis from ambient nitrate/nitrite reduction

Chem, Год журнала: 2023, Номер 9(7), С. 1768 - 1827

Опубликована: Июнь 21, 2023

Язык: Английский

---

Electrochemical Nitrate Reduction: Ammonia Synthesis and the Beyond

Advanced Materials, Год журнала: 2023, Номер 36(17)

Опубликована: Июнь 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

Язык: Английский

---

Dynamic Reconstitution Between Copper Single Atoms and Clusters for Electrocatalytic Urea Synthesis

Advanced Materials, Год журнала: 2023, Номер 35(18)

Опубликована: Фев. 6, 2023

Electrocatalytic CN coupling between carbon dioxide and nitrate has emerged to meet the comprehensive demands of footprint closing, valorization waste, sustainable manufacture urea. However, identification catalytic active sites design efficient electrocatalysts remain a challenge. Herein, synthesis urea catalyzed by copper single atoms decorated on CeO2 support (denoted as Cu1 -CeO2 ) is reported. The catalyst exhibits an average yield rate 52.84 mmol h-1 gcat.-1 at -1.6 V versus reversible hydrogen electrode. Operando X-ray absorption spectra demonstrate reconstitution (Cu1 clusters (Cu4 during electrolysis. These electrochemically reconstituted Cu4 are real for electrocatalytic synthesis. Favorable reactions formation validated using operando synchrotron-radiation Fourier transform infrared spectroscopy theoretical calculations. Dynamic transformations single-atom configurations occur when applied potential switched open-circuit potential, endowing with superior structural electrochemical stabilities.

Язык: Английский

---

Breaking Local Charge Symmetry of Iron Single Atoms for Efficient Electrocatalytic Nitrate Reduction to Ammonia

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(39)

Опубликована: Июль 22, 2023

The electrochemical conversion of nitrate pollutants into value-added ammonia is a feasible way to achieve artificial nitrogen cycle. However, the development electrocatalytic nitrate-to-ammonia reduction reaction (NO3- RR) has been hampered by high overpotential and low Faradaic efficiency. Here we develop an iron single-atom catalyst coordinated with phosphorus on hollow carbon polyhedron (denoted as Fe-N/P-C) NO3- RR electrocatalyst. Owing tuning effect atoms breaking local charge symmetry single-Fe-atom catalyst, it facilitates adsorption ions enrichment some key intermediates during process. Fe-N/P-C exhibits 90.3 % efficiency yield rate 17980 μg h-1 mgcat-1 , greatly outperforming reported Fe-based catalysts. Furthermore, operando SR-FTIR spectroscopy measurements reveal pathway based observed under different applied potentials durations. Density functional theory calculations demonstrate that optimized free energy ascribed asymmetric atomic interface configuration, which achieves optimal electron density distribution. This work demonstrates critical role atomic-level precision modulation heteroatom doping for RR, providing effective strategy improving catalytic performance single atom catalysts in reactions.

Язык: Английский

---

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

Inorganic Chemistry Frontiers, Год журнала: 2023, Номер 10(12), С. 3489 - 3514

Опубликована: Янв. 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.

Язык: Английский

---

Iron Nanoparticles Protected by Chainmail‐structured Graphene for Durable Electrocatalytic Nitrate Reduction to Nitrogen

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(5)

Опубликована: Дек. 5, 2022

Abstract The electrochemical nitrate reduction reaction (NO 3 RR) is an appealing technology for regulating the nitrogen cycle. Metallic iron one of well‐known electrocatalysts NO RR, but it suffers from poor durability due to leaching and oxidation during electrocatalytic process. In this work, a graphene‐nanochainmail‐protected nanoparticle (Fe@Gnc) electrocatalyst reported. It displays superior removal efficiency high selectivity. Notably, catalyst delivers exceptional stability durability, with rate selectivity remained ≈96 % that first time after up 40 cycles (24 h cycle). As expected, conductive graphene nanochainmail provides robust protection internal active sites, allowing Fe@Gnc maintain its long‐lasting catalytic activity. This research proposes workable solution scientific challenge lasting ability iron‐based in large‐scale industrialization.

Язык: Английский

---

Dual‐Site W‐O‐CoP Catalysts for Active and Selective Nitrate Conversion to Ammonia in a Broad Concentration Window

Advanced Materials, Год журнала: 2023, Номер 35(32)

Опубликована: Июнь 24, 2023

Environmentally friendly electrochemical reduction of contaminated nitrate to ammonia (NO3- RR) is a promising solution for large quantity (NH3 ) production, which, however, complex multi-reaction process involving coordination between different reaction intermediates and water decomposition-provided active hydrogen (Hads species. Here, dual-site catalyst [W-O] group-doped CoP nanosheets (0.6W-O-CoP@NF) has been designed synergistically catalyze the NO3- RR decomposition, especially reactions Hads This catalytic exhibits an extremely high NH3 yield 80.92 mg h-1 cm-2 Faradaic efficiency (FE) 95.2% in 1 m KOH containing 0.1 . Significantly, 0.6W-O-CoP@NF presents greatly enhanced FE wide concentration ranges 0.001-0.1 compared reported. The excellent performance attributed synergistic effect sites, which doped group promotes decomposition supply abundant , meanwhile modulates electronic structure Co strengthened adsorption (H2 release prevention, resultantly facilitating RR. Finally, Zn-NO3- battery assembled simultaneously achieve three functions: electricity output, treatment wastewater.

Язык: Английский

---

Potential-Induced Synthesis and Structural Identification of Oxide-Derived Cu Electrocatalysts for Selective Nitrate Reduction to Ammonia

ACS Catalysis, Год журнала: 2023, Номер 13(11), С. 7529 - 7537

Опубликована: Май 19, 2023

Developing effective electrocatalysts for nitrate reduction to ammonia is paramount synthesis while addressing the water pollutant issue. Identifying active structure and its correlation with catalytic behavior during reaction process essential challenging rational design of advanced electrocatalysts. Herein, starting from Cu2O particles controllable crystal facets, electrochemically reconstituted Cu/Cu2O was fabricated as a suitable system, relationship between chemical state copper product selectivity in studied. At −0.9 V versus reversible hydrogen electrode, oxide-derived Cu0 (OD-Cu) cube achieved high Faradaic efficiency 93.9% productivity up 219.8 μmol h–1 cm–2, surpassing those most Cu-based catalysts. In situ Raman analysis, well-designed pulsed electrolysis experiments, theoretical calculations showed that preferentially produced on OD-Cu at potentials presence interface favored nitrite formation low potentials. The originated enhanced adsorption lower barrier potential-determining step (*NH3 → NH3). This work presents an strategy boost electrocatalysis offers insight into real phase corresponding

Язык: Английский

---

N‐Coordinated Cu–Ni Dual‐Single‐Atom Catalyst for Highly Selective Electrocatalytic Reduction of Nitrate to Ammonia

Small, Год журнала: 2023, Номер 19(20)

Опубликована: Фев. 15, 2023

As a traditional method of ammonia (NH3 ) synthesis, Haber-Bosch expends vast amount energy. An alternative route for NH3 synthesis is proposed from nitrate (NO3- via electrocatalysis. However, the structure-activity relationship remains challenging and requires in-depth research both experimentally theoretically. Here an N-coordinated Cu-Ni dual-single-atom catalyst anchored in N-doped carbon (Cu/Ni-NC) reported, which has competitive activity with maximal Faradaic efficiency 97.28%. Detailed characterizations demonstrate that high Cu/Ni-NC mainly comes contribution dual active sites. That is, (1) electron transfer (Ni → Cu) reveals strong interaction dual-single-atom; (2) hybridizations Cu 3d-and Ni 3d-O 2p orbitals NO3- can accelerate dual-site to ; (3) effectively decrease rate-limiting step barriers, suppress N-N coupling N2 O formation hydrogen production.

Язык: Английский

---

Highly Efficient Electrochemical Nitrate Reduction to Ammonia in Strong Acid Conditions with Fe₂M‐Trinuclear‐Cluster Metal–Organic Frameworks

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(27)

Опубликована: Май 10, 2023

Nitrate-containing industrial wastewater poses a serious threat to the global food security and public health safety. As compared traditional microbial denitrification, electrocatalytic nitrate reduction shows better sustainability with ultrahigh energy efficiency production of high-value ammonia (NH3 ). However, nitrate-containing from most processes, such as mining, metallurgy, petrochemical engineering, is generally acidic, which contradicts typical neutral/alkaline working conditions for both denitrifying bacteria state-of-the-art inorganic electrocatalysts, leading demand pre-neutralization problematic hydrogen evaluation reaction (HER) competition catalyst dissolution. Here, we report series Fe2 M (M=Fe, Co, Ni, Zn) trinuclear cluster metal-organic frameworks (MOFs) that enable highly efficient ammonium under strong acidic excellent stability. In pH=1 electrolyte, Co-MOF demonstrates NH3 yield rate 20653.5 μg h-1 mg-1site 90.55 % -Faradaic (FE), 98.5 -selectivity up 75 hr Additionally, successful in high-acidic directly produce sulfate nitrogen fertilizer, avoiding subsequent aqueous extraction preventing spillage loss. This cluster-based MOF structures provide new insights into design principles high-performance catalysts environmentally-relevant conditions.

Язык: Английский

---