Accelerating Industrial‐Level NO3− Electroreduction to Ammonia on Cu Grain Boundary Sites via Heteroatom Doping Strategy DOI
Yan Wang,

Shuai Xia,

Rui Cai

и другие.

Small, Год журнала: 2023, Номер 19(26)

Опубликована: Май 17, 2023

Although the electrocatalytic nitrate reduction reaction (NO3- RR) is an attractive NH3 synthesis route, it suffers from low yield due to lack of efficient catalysts. Here, this work reports a novel grain boundary (GB)-rich Sn-Cu catalyst, derived in situ electroreduction Sn-doped CuO nanoflower, for effectively electrochemical converting NO3- . The optimized Sn1% -Cu electrode achieves high rate 1.98 mmol h-1 cm-2 with industrial-level current density -425 mA at -0.55 V versus reversible hydrogen (RHE) and maximum Faradaic efficiency 98.2% -0.51 RHE, outperforming pure Cu electrode. In Raman attenuated total reflection Fourier transform infrared spectroscopies reveal pathway RR by monitoring adsorption property intermediates. Density functional theory calculations clarify that high-density GB active sites competitive evolution (HER) suppression induced Sn doping synergistically promote highly selective RR. This paves avenue over catalyst reconstruction heteroatom doping.

Язык: Английский

Intermediates Regulation via Electron‐Deficient Cu Sites for Selective Nitrate‐to‐Ammonia Electroreduction DOI Open Access
Zhengxiang Gu, Yechuan Zhang,

Xuelian Wei

и другие.

Advanced Materials, Год журнала: 2023, Номер 35(48)

Опубликована: Сен. 21, 2023

Ammonia (NH3 ), known as one of the fundamental raw materials for manufacturing commodities such chemical fertilizers, dyes, ammunitions, pharmaceuticals, and textiles, exhibits a high hydrogen storage capacity ≈17.75%. Electrochemical nitrate reduction (NO3 RR) to valuable ammonia at ambient conditions is promising strategy facilitate artificial nitrogen cycle. Herein, copper-doped cobalt selenide nanosheets with selenium vacancies are reported robust highly efficient electrocatalyst ammonia, exhibiting maximum Faradaic efficiency ≈93.5% an yield rate 2360 µg h-1 cm-2 -0.60 V versus reversible electrode. The in situ spectroscopical theoretical study demonstrates that incorporation Cu dopants Se into efficiently enhances electron transfer from Co atoms via bridging atoms, forming electron-deficient structure sites accelerate NO3- dissociation stabilize *NO2 intermediates, eventually achieving selective catalysis entire NO3 RR process produce efficiently.

Язык: Английский

Процитировано

65
Dopant‐Induced Electronic States Regulation Boosting Electroreduction of Dilute Nitrate to Ammonium DOI
Lu‐Hua Zhang,

Yangting Jia,

Jiayu Zhan

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(22)

Опубликована: Март 29, 2023

Electrochemically converting NO3- into NH3 offers a promising route for water treatment. Nevertheless, electroreduction of dilute is still suffering from low activity and/or selectivity. Herein, B as modifier was introduced to tune electronic states Cu and further regulate the performance electrochemical reduction reaction (NO3 RR) with concentration (≤100 ppm -N). Notably, linear relationship established by plotting yield vs. oxidation state Cu, indicating that increase Cu+ content leads an enhanced -to-NH3 conversion activity. Under -N 100 ppm, optimal Cu(B) catalyst displays % at -0.55 -0.6 V RHE, record-high 309 mmol h-1 gcat-1 , which more than 25 times compared pristine nanoparticles (12 ). This research provides effective method has certain guiding significance efficient green wastewater in future.

Язык: Английский

Процитировано

59
Enhanced Nitrate‐to‐Ammonia Efficiency over Linear Assemblies of Copper‐Cobalt Nanophases Stabilized by Redox Polymers DOI Creative Commons
Wenhui He, Shubhadeep Chandra, Thomas Quast

и другие.

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

Опубликована: Май 26, 2023

Renewable electricity-powered nitrate (NO3- ) reduction reaction (NO3 RR) offers a net-zero carbon route to the realization of high ammonia (NH3 productivity. However, this suffers from low energy efficiency (EE, with half-cell EE commonly <36%), since overpotentials are required overcome weak NO3- binding affinity and sluggish NO3 RR kinetics. To alleviate this, rational catalyst design strategy that involves linear assembly sub-5 nm Cu/Co nanophases into sub-20 thick nanoribbons is suggested. The theoretical experimental studies show Cu-Co nanoribbons, similar enzymes, enable strong adsorption rapid tandem catalysis NH3 , owing their richly exposed binary phase boundaries adjacent sites at distance. In situ Raman spectroscopy further reveals applied overpotentials, rapidly activated subsequently stabilized by specifically designed redox polymer in scavenges intermediately formed highly oxidative nitrogen dioxide (NO2 ). As result, stable current density ≈450 mA cm-2 achieved, Faradaic >97% for formation an unprecedented ≈42%.

Язык: Английский

Процитировано

50
Electrochemical nitrate reduction to ammonia with cation shuttling in a solid electrolyte reactor DOI
Feng-Yang Chen, Ahmad Elgazzar, Stephanie Pecaut

и другие.

Nature Catalysis, Год журнала: 2024, Номер 7(9), С. 1032 - 1043

Опубликована: Авг. 12, 2024

Язык: Английский

Процитировано

45
Electrocatalytic upgrading of nitrogenous wastes into value-added chemicals: A review DOI
Jiawei Liu, Zeyu Li, Chade Lv

и другие.

Materials Today, Год журнала: 2024, Номер 73, С. 208 - 259

Опубликована: Фев. 7, 2024

Язык: Английский

Процитировано

39
Ambient Electrochemical Ammonia Synthesis: From Theoretical Guidance to Catalyst Design DOI Creative Commons

Jianjia Mu,

Xuan‐Wen Gao,

Tong Yu

и другие.

Advanced Science, Год журнала: 2024, Номер 11(15)

Опубликована: Фев. 12, 2024

Abstract Ammonia, a vital component in the synthesis of fertilizers, plastics, and explosives, is traditionally produced via energy‐intensive environmentally detrimental Haber–Bosch process. Given its considerable energy consumption significant greenhouse gas emissions, there growing shift toward electrocatalytic ammonia as an eco‐friendly alternative. However, developing efficient electrocatalysts capable achieving high selectivity, Faraday efficiency, yield under ambient conditions remains challenge. This review delves into decades‐long research synthesis, highlighting evolution fundamental principles, theoretical descriptors, reaction mechanisms. An in‐depth analysis nitrogen reduction (NRR) nitrate (NitRR) provided, with focus on their electrocatalysts. Additionally, theories behind electrocatalyst design for are examined, including Gibbs free approach, Sabatier principle, d ‐band center theory, orbital spin states. The culminates comprehensive overview current challenges prospective future directions development NRR NitRR, paving way more sustainable methods production.

Язык: Английский

Процитировано

39
Modulating the Electrolyte Microenvironment in Electrical Double Layer for Boosting Electrocatalytic Nitrate Reduction to Ammonia DOI

Weidong Wen,

Shidong Fang,

Yitong Zhou

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(32)

Опубликована: Май 29, 2024

Abstract Electrochemical nitrate reduction reaction (NO 3 RR) is a promising approach to achieve remediation of nitrate‐polluted wastewater and sustainable production ammonia. However, it still restricted by the low activity, selectivity Faraday efficiency for ammonia synthesis. Herein, we propose an effective strategy modulate electrolyte microenvironment in electrical double layer (EDL) mediating alkali metal cations enhance NO RR performance. Taking bulk Cu as model catalyst, experimental study reveals that − ‐to‐NH performance different electrolytes follows trend Li + <Cs <Na <K . Theoretical studies illustrate proton transport rate activity rate‐determining step 2 ) increase order The cation effects are also general two typical nanostructured catalysts including copper/cuprous oxide nickel phosphides, achieving near‐100 % Faradaic over 99 conversion NH Furthermore, demonstrate can be converted high‐purity 4 Cl catalyst K ‐containing electrolyte.

Язык: Английский

Процитировано

33
Enhancing Compatibility of Two‐Step Tandem Catalytic Nitrate Reduction to Ammonia Over P‐Cu/Co(OH)2 DOI

Qiuyu Yan,

Rundong Zhao, Lihong Yu

и другие.

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 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.

Язык: Английский

Процитировано

31
Modulating the Surface Concentration and Lifetime of Active Hydrogen in Cu-Based Layered Double Hydroxides for Electrocatalytic Nitrate Reduction to Ammonia DOI
Hongmei Li, S Li,

Renjun Guan

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(16), С. 12042 - 12050

Опубликована: Июль 29, 2024

Strategies incorporating heterometals to introduce surface-active hydrogen (*H) have been extensively utilized enhance the electrocatalytic activity of Cu-based catalysts in nitrate reduction reaction (NitRR). However, a comprehensive understanding *H behavior and its specific impact on regulating NitRR pathway remains elusive, particularly quantitative manner. In this study, we prepared group layered double hydroxides (LDHs) as model with diverse concentrations lifetimes. Our findings reveal that LDHs is highly dependent species could be modulated by incorporated heterometallic sites. Specifically, conducted situ analysis different LDH using time-resolved scanning electrochemical microscopy. The surface concentration lifetime at various applied potentials were quantified, enabling us establish relationship between performance. Therefore, optimal performance was achieved CuNi-LDHs, exhibiting faradaic efficiency 94.6% yield rate 2.7 mg h–1 cm–2 because appropriate lifetime. Additionally, observe trend CuNi > CuCo Cu CuRu CuFe CuMg terms for NH3 production. These results suggest effectively utilizing stable produced catalyst, one would allow favorable performance, offering promising strategy other hydrogenation reactions.

Язык: Английский

Процитировано

28
Synergism of electrostatic attraction and tandem catalytic effect enabled efficient electrosynthesis of ammonia from a wide-range of nitrate concentrations DOI

Youwei Sheng,

Ruidong Yang,

Keke Shi

и другие.

Chemical Engineering Journal, Год журнала: 2024, Номер 485, С. 149769 - 149769

Опубликована: Фев. 16, 2024

Язык: Английский

Процитировано

27