Regulating the Electrochemical Nitrate Reduction Performance with Controllable Distribution of Unconventional Phase Copper on Alloy Nanostructures DOI Creative Commons
Yuecheng Xiong, Yunhao Wang, Mingzi Sun

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 6, 2024

Abstract Electrochemical nitrate reduction reaction (NO 3 RR) is emerging as a promising strategy for removal and ammonia (NH ) production using renewable electricity. Although great progresses have been achieved, the crystal phase effect of electrocatalysts on NO RR remains rarely explored. Here, epitaxial growth unconventional 2H Cu hexagonal close‐packed ( hcp IrNi template, resulting in formation three IrNiCu@Cu nanostructures, reported. IrNiCu@Cu‐20 shows superior catalytic performance, with NH Faradaic efficiency (FE) 86% at −0.1 (vs reversible hydrogen electrode [RHE]) yield rate 687.3 mmol g −1 h , far better than common face‐centered cubic Cu. In sharp contrast, IrNiCu@Cu‐30 IrNiCu@Cu‐50 covered by shell display high selectivity toward nitrite 2 − ), FE above 60% 0.1 RHE). Theoretical calculations demonstrated that has optimal electronic structures due to highest d‐band center strongest trend lowest energy barriers. The electroactivity originates from abundant low coordination sites surface, which guarantees fast electron transfer accelerate intermediate conversions. This work provides feasible tactic regulate product distribution engineering electrocatalysts.

Language: Английский

Selective Electrocatalytic Conversion of Nitric Oxide to High Value‐Added Chemicals DOI Creative Commons
Dongdong Wang, Xue Feng Lu, Deyan Luan

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(18)

Published: Jan. 25, 2024

The artificial disturbance in the nitrogen cycle has necessitated an urgent need for nitric oxide (NO) removal. Electrochemical technologies NO conversion have gained increasing attention recent years. This comprehensive review presents advancements selective electrocatalytic of to high value-added chemicals, with specific emphasis on catalyst design, electrolyte composition, mass diffusion, and adsorption energies key intermediate species. Furthermore, explores synergistic electrochemical co-electrolysis carbon source molecules, enabling synthesis a range valuable chemicals C─N bonds. It also provides in-depth insights into intricate reaction pathways underlying mechanisms, offering perspectives challenges prospects electrolysis. By advancing comprehension fostering awareness balance, this contributes development efficient sustainable systems from NO.

Language: Английский

Citations

29
Sustainable Electrosynthesis of Cyclohexanone Oxime through Nitrate Reduction on a Zn–Cu Alloy Catalyst DOI Creative Commons
Jonathan Sharp,

Anna Ciotti,

Hayley G. Andrews

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3287 - 3297

Published: Feb. 15, 2024

Cyclohexanone oxime is an important precursor for Nylon-6 and typically synthesized via the nucleophilic addition–elimination of hydroxylamine with cyclohexanone. Current technologies production are, however, not environment-friendly due to requirement harsh reaction conditions. Here, we report electrochemical method one-pot synthesis cyclohexanone under ambient conditions aqueous nitrate as nitrogen source. A series Zn–Cu alloy catalysts are developed drive reduction nitrate, where intermediate formed in electroreduction process can undergo a chemical present electrolyte produce corresponding oxime. The best performance achieved on Zn93Cu7 electrocatalyst 97% yield 27% Faradaic efficiency at 100 mA/cm2. By analyzing catalytic activities/selectivities different alloys conducting in-depth mechanistic studies situ Raman spectroscopy theoretical calculations, demonstrate that adsorption species plays central role performance. Overall, this work provides attractive strategy build C–N bond organic through reduction, while highlighting importance controlling surface product selectivity electrosynthesis.

Language: Английский

Citations

23
Enhancing Compatibility of Two‐Step Tandem Catalytic Nitrate Reduction to Ammonia Over P‐Cu/Co(OH)2 DOI

Qiuyu Yan,

Rundong Zhao, Lihong Yu

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 11, 2024

Abstract Electrochemical nitrate reduction reaction (NO 3 RR) is a promising approach to realize ammonia generation and wastewater treatment. However, the transformation from NO − NH involves multiple proton‐coupled electron transfer processes by‐products 2 , H etc.), making high selectivity challenge. Herein, two‐phase nanoflower P‐Cu/Co(OH) electrocatalyst consisting of P‐Cu clusters P‐Co(OH) nanosheets designed match two‐step tandem process ) more compatible, avoiding excessive accumulation optimizing whole reaction. Focusing on initial 2e process, inhibited * desorption Cu sites in gives rise appropriate released electrolyte. Subsequently, exhibits superior capacity for trapping transforming desorbed during latter 6e due thermodynamic advantage contributions active hydrogen. In 1 m KOH + 0.1 leads yield rate 42.63 mg h cm Faradaic efficiency 97.04% at −0.4 V versus reversible hydrogen electrode. Such well‐matched achieves remarkable synthesis performance perspective catalytic reaction, offering novel guideline design RR electrocatalysts.

Language: Английский

Citations

23
Recent Progress and Perspectives on Transition Metal-Based Electrocatalysts for Efficient Nitrate Reduction DOI
Jun Zhou,

Sanshuang Gao,

Guangzhi Hu

et al.

Energy & Fuels, Journal Year: 2024, Volume and Issue: 38(8), P. 6701 - 6722

Published: April 8, 2024

Electrochemical nitrate reduction is the process of converting into ammonia or nitrogen using electric energy. This saves energy, protects environment, and an important technology for resource recovery water purification. paper examines recent advances in electrochemical research analyzes reaction mechanism path as well influence various factors on through thermodynamic kinetic principles. Second, catalytic performances transition metal electrocatalysts form single metals, alloys, oxides, composites are analyzed detail, which lays foundation rational development new, efficient, stable electrocatalysts. Finally, future directions prospects envisioned.

Language: Английский

Citations

20
Optimizing Intermediate Adsorption over PdM (M=Fe, Co, Ni, Cu) Bimetallene for Boosted Nitrate Electroreduction to Ammonia DOI
Yuanbo Zhou, Lifang Zhang, Zebin Zhu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(18)

Published: March 7, 2024

Abstract Electrochemical reduction of nitrate to ammonia (NO 3 RR) is a promising and eco‐friendly strategy for production. However, the sluggish kinetics eight‐electron transfer process poor mechanistic understanding strongly impedes its application. To unveil internal laws, herein, library Pd‐based bimetallene with various transition metal dopants (PdM (M=Fe, Co, Ni, Cu)) are screened learn their structure–activity relationship towards NO RR. The ultra‐thin structure metallene greatly facilitates exposure active sites, metals break electronic balance upshift d‐band center, thus optimizing intermediates adsorption. anisotropic characteristics these make RR activity in order PdCu>PdCo≈PdFe>PdNi>Pd, record‐high NH yield rate 295 mg h −1 cat along Faradaic efficiency 90.9 % achieved neutral electrolyte on PdCu bimetallene. Detailed studies further reveal that moderate N‐species (*NO *NO 2 ) adsorption ability, enhanced activation, reduced HER facilitate We believe our results will give systematic guidance future design catalysts.

Language: Английский

Citations

17
Co‐Catalytic Metal‐Support Interactions Design on Single‐Atom Alloy for Boosted Electro‐Reduction of Nitrate to Nitrogen DOI
Ziyang Wu, Xuxin Kang, Sen Wang

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(45)

Published: May 28, 2024

Abstract The past decades have seen considerable imbalances in the nitrogen cycle due to excessive use of nitrate agriculture and industry. Electrocatalytic reduction (NO 3 RR) (N 2 ) holds significant potential for addressing pollution wastewater but suffers from nitrite formation sluggish hydrogeneration process. Here a single atom alloy (SAA) catalyst featuring atomically dispersed Ru on 2D Ni metal (Ru 1 Ni), proving remarkable performance − –N conversion (≈93%) N selectivity (≈99%)) through co‐catalytic metal‐support interactions (CMSI) effect is reported. Significantly, SAA achieves NO RR removal capacity as high 11.1 mg L −1 h cm −2 with 20 cycles stability (9 per cycle), surpassing most previously reported works. core boosting lies synergistically promoted activation accelerated hydrogenation oxide intermediates site substrate, respectively, revealed by various situ experiments theoretical simulations. DFT calculations indicate electron transfer substrate more robust interaction between Ru–Ni comparison that Ni–Ni. This work offers resilient methodology rational design highly efficient electrocatalysts CMSI modulation RR, illuminating arena treatment cycle.

Language: Английский

Citations

17
High-valent cobalt active sites derived from electrochemical activation of metal-organic frameworks for efficient nitrate reduction to ammonia DOI Open Access

Jinyan Yang,

Wenda Zhang, Han Zhao

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 340, P. 123237 - 123237

Published: Aug. 29, 2023

Language: Английский

Citations

33
Tungsten Nitride/Tungsten Oxide Nanosheets for Enhanced Oxynitride Intermediate Adsorption and Hydrogenation in Nitrate Electroreduction to Ammonia DOI

Zhencong Huang,

Baopeng Yang,

Yulong Zhou

et al.

ACS Nano, Journal Year: 2023, Volume and Issue: 17(24), P. 25091 - 25100

Published: Dec. 6, 2023

Electrochemical NO3– reduction reaction (NO3RR) is a promising technique for green NH3 synthesis. Tungsten oxide (WO3) has been regarded as an effective electrocatalyst electrochemical However, the weak adsorption and sluggish hydrogenation of oxynitride intermediates (NOx, e.g., *NO3 *NO2) over WO3 materials hinder efficiency converting to NH3. Herein, we design heterostructure tungsten nitride (WN) (WN/WO3) nanosheets optimize *NO2 adsorptions facilitate hydrogenations achieve highly efficient NO3RR produce Theoretical calculations predict that locally introducing WN into will shorten distance between adjacent W atoms, resulting in being strongly adsorbed on active sites form bidentate ligands instead relatively monodentate ligands. Furthermore, facilitates H2O dissociation supply requisite protons, which beneficial hydrogenations. Inspired by theoretical prediction, WN/WO3 are successfully fabricated through high-temperature nitridation process. The transmission electron microscopy, X-ray photoelectron spectroscopy, absorption near-edge spectroscopy investigations confirm amorphous introduced situ composite heterostructure. as-prepared exhibit high Faraday 88.9 ± 7.2% appreciable yield rate 8.4 mg h–1 cm–2 toward production, much higher than individual WN. enhanced behaviors *NOx characterized Fourier-transform infrared consistent with predictions. This work develops facile nanomaterials tune NOx boosting from

Language: Английский

Citations

31
Mesostructures Engineering to Promote Selective Nitrate‐to‐Ammonia Electroreduction DOI

Lizhi Sun,

Huiqin Yao, Yanzhi Wang

et al.

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(44)

Published: Oct. 10, 2023

Abstract The electroreduction of nitrate into green ammonia (NO 3 − ‐to‐NH ) in aqueous solution represents a sustainable route applicable to NH electrosynthesis and nitrogen balance. However, the NO undergoes complex eight electron (8e transfer pathway results unsatisfying activity selectivity. Here, mesostructures engineering is presented as new robust design strategy for producing high‐performance multimetallic electrocatalysts that remarkably promote selective electroreduction. 1D PdCuAg mesoporous nanotubes (MTs) are facilely prepared by one‐step galvanic replacement‐assisted surfactant‐templating method an solution. electrocatalyst shows remarkable performance with high Faradaic efficiency (FE NH3 95.2%, superior yield rate 17.7 mg h −1 , impressive energy 29.8%, outstanding stability (50 cycles), all which much better than counterpart electrocatalysts. promotion comes from electron‐rich surface nanoconfinement microenvironment mesostructured synergies enrich nanozyme‐like chemisorption key intermediates thus facilitates through 8e reaction pathway. Meanwhile,1D MTs practically explored Zn‐NO battery, delivering 25.85 µmol cm −2 FE 92.4%.

Language: Английский

Citations

28
Recent developments in designing Cu-based electrocatalysts and advanced strategies for electrochemical nitrate reduction to ammonia DOI
Sadeeq Ullah, Shiyong Wang, Changping Li

et al.

Journal of environmental chemical engineering, Journal Year: 2023, Volume and Issue: 11(5), P. 110927 - 110927

Published: Sept. 4, 2023

Language: Английский

Citations

27