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

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Urea Electrosynthesis from Nitrate and CO₂ on Diatomic Alloys

Advanced Materials, Год журнала: 2024, Номер 36(30)

Опубликована: Июнь 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.

Язык: Английский

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Carbon‐Anchored Molybdenum Oxide Nanoclusters as Efficient Catalysts for the Electrosynthesis of Ammonia and Urea

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(19)

Опубликована: Март 13, 2023

Abstract The electrochemical NO 3 − reduction and its coupling with CO 2 can provide novel clean routes to synthesize NH urea, respectively. However, their practical application is still impeded by the lack of efficient catalysts desirable Faradaic efficiency (FE) yield rate. Herein, we report synthesis molybdenum oxide nanoclusters anchored on carbon black (MoO x /C) as electrocatalyst. It affords an outstanding FE 98.14 % rate 91.63 mg h −1 cat. in reduction. Besides, highest 27.7 a maximum urea 1431.5 μg toward also achieved. formation electron‐rich MoO highly unsaturated metal sites /C heterostructure beneficial for enhanced catalytic performance. Studies mechanism reveal that stabilization *NO *CO NOOH intermediates are critical synthesis,

Язык: Английский

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Review on strategies for improving the added value and expanding the scope of CO₂ electroreduction products

Chemical Society Reviews, Год журнала: 2024, Номер 53(10), С. 5149 - 5189

Опубликована: Янв. 1, 2024

This review summarizes promising strategies including the design of catalysts and construction coupled electrocatalytic reaction systems, aimed at achieving selective production various products from CO 2 electroreduction.

Язык: Английский

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Toward effective electrocatalytic C–N coupling for the synthesis of organic nitrogenous compounds using CO₂ and biomass as carbon sources

SusMat, Год журнала: 2023, Номер 3(6), С. 781 - 820

Опубликована: Дек. 1, 2023

Abstract Thermochemical conversion of fossil resources into fuels, chemicals, and materials has rapidly increased atmospheric CO 2 levels, hindering global efforts toward achieving carbon neutrality. With the increasing push for sustainability, utilizing electrochemical technology to transform or biomass value‐added chemicals close cycle with sustainable energy sources represents a promising strategy. Expanding scope electrosynthesis is prerequisite electrification chemical manufacturing. To this end, constructing C─N bond considered priority. However, systematic review electrocatalytic processes building bonds using as not available. Accordingly, highlights research progress in organic nitrogen compounds from by coupling reactions view catalytic materials, focusing on enlightenment traditional catalysis understanding basis coupling. The possibility electrocatalysis also examined standpoints activation substrates, site, mechanism, inhibition hydrogen evolution reaction (HER). Finally, challenges prospects improved efficiency selectivity future development are discussed.

Язык: Английский

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Electrochemical NO₃^– Reduction Catalyzed by Atomically Precise Ag₃₀Pd₄ Bimetallic Nanocluster: Synergistic Catalysis or Tandem Catalysis?

ACS Nano, Год журнала: 2023, Номер 17(13), С. 12747 - 12758

Опубликована: Июнь 28, 2023

Electrochemically converting NO3- compounds into ammonia represents a sustainable route to remove industrial pollutants in wastewater and produce valuable chemicals. Bimetallic nanomaterials usually exhibit better catalytic performance than the monometallic counterparts, yet unveiling reaction mechanism is extremely challenging. Herein, we report an atomically precise [Ag30Pd4 (C6H9)26](BPh4)2 (Ag30Pd4) nanocluster as model catalyst toward electrochemical reduction (eNO3-RR) elucidate different role of Ag Pd site unveil comprehensive mechanism. Ag30Pd4 homoleptic alkynyl-protected superatom with 2 free electrons, it has metal core where 4 atoms are located at subcenter core. Furthermore, exhibits excellent eNO3-RR robust stability for prolonged operation, can achieve highest Faradaic efficiency NH3 over 90%. In situ Fourier-transform infrared study revealed that plays more critical NO2-, while makes major contribution catalyze NO2- NH3. The bimetallic adopts tandem rather synergistic effect eNO3-RR. Such finding was further confirmed by density functional theory calculations, they disclosed most preferable binding NO3-, which then binds water molecule release NO2-. Subsequently, transfer vicinal exposed promote formation.

Язык: Английский

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Electrocatalytic synthesis of C–N coupling compounds from CO₂ and nitrogenous species

SusMat, Год журнала: 2024, Номер 4(2)

Опубликована: Март 12, 2024

Abstract The electrocatalytic synthesis of C–N coupling compounds from CO 2 and nitrogenous species not only offers an effective avenue to achieve carbon neutrality reduce environmental pollution, but also establishes a route synthesize valuable chemicals, such as urea, amide, amine. This innovative approach expands the application range product categories beyond simple carbonaceous in reduction, which is becoming rapidly advancing field. review summarizes research progress urea synthesis, using N , NO − 3 species, explores emerging trends electrosynthesis amide amine nitrogen species. Additionally, future opportunities this field are highlighted, including amino acids other containing bonds, anodic reactions water oxidation, catalytic mechanism corresponding reactions. critical captures insights aimed at accelerating development electrochemical reactions, confirming superiority method over traditional techniques.

Язык: Английский

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Dynamic Reconstruction of Two‐Dimensional Defective Bi Nanosheets for Efficient Electrocatalytic Urea Synthesis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(16)

Опубликована: Фев. 22, 2024

Abstract Abstract:Catalyst surface dynamics drive the generation of active species for electrocatalytic reactions. Yet, understanding dominant site formation and reaction mechanisms is limited. In this study, we thoroughly investigate dynamic reconstruction two‐dimensional defective Bi nanosheets from exfoliated 2 Se 3 under electrochemical CO nitrate (NO − ) reduction conditions. The ultrathin obtained by NaBH 4 ‐assisted cryo‐mediated liquid‐phase exfoliation are more easily reduced reconstructed to with high‐density grain boundaries (GBs; GB‐rich Bi). catalyst affords a remarkable yield rate 4.6 mmol h −1 mg cat. Faradaic efficiency 32 % urea production at −0.40 V vs. RHE. Notably, 8.2 times higher than those low‐GB bulk catalysts, respectively. Theoretical analysis demonstrates that GB sites significantly reduce *CO *NH intermediate energy C−N coupling barrier, enabling selective electrosynthesis on catalyst. This work will trigger further research into structure‐activity interplay in processes using situ techniques.

Язык: Английский

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A Strongly Coupled Metal/Hydroxide Heterostructure Cascades Carbon Dioxide and Nitrate Reduction Reactions toward Efficient Urea Electrosynthesis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(48)

Опубликована: Сен. 7, 2024

Abstract The direct coupling of nitrate ions and carbon dioxide for urea synthesis presents an appealing alternative to the Bosch–Meiser process in industry. simultaneous activation nitrate, however, as well efficient C−N on single active site, poses significant challenges. Here, we propose a novel metal/hydroxide heterostructure strategy based synthesizing Ag−CuNi(OH) 2 composite cascade reduction reactions electrosynthesis. strongly coupled interface integrates two distinct sites activation, facilitates *CO (on silver, where * denotes site) *NH hydroxide) formation. Moreover, optimizes water splitting supply hydrogen atoms, thereby expediting deoxyreduction processes essential Consequently, our delivers high yield rate 25.6 mmol g cat. −1 h Faradaic efficiency 46.1 %, excellent cycling stability. This work provides new insights into design dual‐site catalysts coupling, considering their role interface.

Язык: Английский

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NH₃ Electrosynthesis from N₂ Molecules: Progresses, Challenges, and Future Perspectives

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(10), С. 6409 - 6421

Опубликована: Фев. 27, 2024

Green ammonia (NH3), made by using renewable electricity to split nearly limitless nitrogen (N2) molecules, is a vital platform molecule and an ideal fuel drive the sustainable development of human society without carbon dioxide emission. The NH3 electrosynthesis field currently faces dilemma low yield rate efficiency; however, decoupling overlapping issues this area providing guidelines for its directions are not trivial because it involves complex reaction process multidisciplinary entries (for example, electrochemistry, catalysis, interfaces, processes, etc.). In Perspective, we introduce classification scheme based on process, namely, direct (N2 reduction reaction) indirect (Li-mediated/plasma-enabled electrosynthesis). This categorization allows us finely decouple complicated pathways identify specific rate-determining steps/bottleneck each synthesis approach such as N2 activation, H2 evolution side reaction, solid-electrolyte interphase engineering, plasma etc. We then present detailed overview latest progresses solving these core in terms whole electrochemical system covering electrocatalysts, electrodes, electrolytes, electrolyzers, Finally, discuss research focuses promising strategies future with multiscale perspective atomistic mechanisms, nanoscale microscale electrodes/interfaces, macroscale electrolyzers/processes. It expected that Perspective will provide readers in-depth understanding bottleneck insightful guidance designing efficient systems.

Язык: Английский

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