Highly Efficient Electrochemical Nitrate and Nitrogen Reduction to Ammonia under Ambient Conditions on Electrodeposited Cu-Nanosphere Electrode

The electrochemical reduction reaction of nitrogenous species such as NO₃⁻ (NO₃RR) and N₂ (NRR) is a promising strategy for producing ammonia under ambient conditions. However, low activity and poor selectivity of both NO₃RR and NRR remain the biggest problem of all current electrocatalysts. In this work, we fabricated Cu-nanosphere film with a high surface area and dominant with a Cu(200) facet by simple electrodeposition method. The Cu-nanosphere film exhibits high electrocatalytic activity for NO₃RR and NRR to ammonia under ambient conditions. In the nitrate environment, the Cu-nanosphere electrode reduced NO₃⁻ to yield NH₃ at a rate of 5.2 mg/h cm², with a Faradaic efficiency of 85 % at −1.3 V. In the N₂-saturated environment, the Cu-nanosphere electrode reduced N₂ to yield NH₃ with the highest yield rate of 16.2 μg/h cm² at −0.5 V, and the highest NH₃ Faradaic efficiency of 41.6 % at −0.4 V. Furthermore, the Cu-nanosphere exhibits excellent stability with the NH₃ yield rate, and the Faradaic efficiency remains stable after 10 consecutive cycles. Such high levels of NH₃ yield, selectivity, and stability at low applied potential are among the best values currently reported in the literature.     

Nanoporous Palladium Hydride for Electrocatalytic N2 Reduction under Ambient Conditions

The electrocatalytic nitrogen reduction reaction (NRR) is an alternative eco‐friendly strategy for sustainable N₂ fixation with renewable energy. However, NRR suffers from sluggish kinetics owing to difficult N₂ adsorption and N≡N cleavage. Now, nanoporous palladium hydride is reported as electrocatalyst for electrochemical N₂ reduction under ambient conditions, achieving a high ammonia yield rate of 20.4 μg h^?1 mg^?1 with a Faradaic efficiency of 43.6 % at low overpotential of 150 mV. Isotopic hydrogen labeling studies suggest the involvement of lattice hydrogen atoms in the hydride as active hydrogen source. In situ Raman analysis and density functional theory (DFT) calculations further reveal the reduction of energy barrier for the rate‐limiting *N₂H formation step. The unique protonation mode of palladium hydride would provide a new insight on designing efficient and robust electrocatalysts for nitrogen fixation.     

A Biomass-Derived Carbon-Based Electrocatalyst for Efficient N2 Fixation to NH3 under Ambient Conditions

Currently, NH₃ production primarily depends on the Haber–Bosch process, which operates at elevated temperatures and pressures and leads to serious CO₂ emissions. Electrocatalytic N₂ reduction offers an environmentally benign approach for the sustainable synthesis of NH₃ under ambient conditions. This work reports the development of biomass-derived amorphous oxygen-doped carbon nanosheet (O−CN) using tannin as the precursor. As a metal-free electrocatalyst for N₂-to-NH₃ conversion, such O−CN shows high catalytic performances, achieving a large NH₃ yield of 20.15 μg h⁻¹ mg⁻¹_cat. and a high Faradic efficiency of 4.97 % at −0.6 V vs. reversible hydrogen electrode (RHE) in 0.1 m HCl at ambient conditions. Remarkably, it also exhibits high electrochemical selectivity and durability.     

Surface Reconstruction of Ultrathin Palladium Nanosheets during Electrocatalytic CO2 Reduction

A surface reconstructing phenomenon is discovered on a defect-rich ultrathin Pd nanosheet catalyst for aqueous CO₂ electroreduction. The pristine nanosheets with dominant (111) facet sites are transformed into crumpled sheet-like structures prevalent in electrocatalytically active (100) sites. The reconstruction increases the density of active sites and reduces the CO binding strength on Pd surfaces, remarkably promoting the CO₂ reduction to CO. A high CO Faradaic efficiency of 93 % is achieved with a site-specific activity of 6.6 mA cm⁻² at a moderate overpotential of 590 mV on the reconstructed 50 nm Pd nanosheets. Experimental and theoretical studies suggest the CO intermediate as a key factor driving the structural transformation during CO₂ reduction. This study highlights the dynamic nature of defective metal nanosheets under reaction conditions and suggests new opportunities in surface engineering of 2D metal nanostructures to tune their electrocatalytic performance.     

Advanced Non-metallic Catalysts for Electrochemical Nitrogen Reduction under Ambient Conditions

The electrochemical reduction of nitrogen into ammonia under ambient conditions is a potential strategy for sustainable ammonia production. At present, one of the main research directions in the field of electrochemical nitrogen fixation is to improve the current efficiency and ammonia yield by developing efficient nitrogen reduction catalysts. To optimise the selectivity and catalytic activity of nitrogen reduction catalysts more efficiently, herein, we systematically summarise the progress of research on nitrogen reduction catalysts in recent years and present some general catalyst design strategies. Considering that it is difficult for metal-based catalysts to balance the competitive reactions of nitrogen activation and hydrogen evolution, we discuss in detail the advantages and application prospects of non-metallic catalysts in electrochemical nitrogen fixation. Moreover, both the design strategy of surface or interface defects, and how this atomic-level control of functionalisation helps to promote selectivity and catalytic activity are also discussed by theoretical and experimental electrochemistry. On this basis, we also discussed the future development direction, opportunities and challenges of nitrogen reduction electrocatalysts.     

环境条件下电催化氮还原的现状、挑战与展望

氨是一种重要的化肥生产原料和清洁能源载体,在工业上主要通过哈伯法合成,但该工艺反应条件苛刻,需要高温高压并消耗大量的化石能源.因此,开发能耗低、反应温和的合成氨方法,对于缓解能源和环境的双重压力具有重要的现实意义.近年来,在温和条件下通过电催化氮还原反应(NRR)合成氨有望替代哈伯法,但该技术的重点在于设计合理的电催化...     

Single‐Atom Catalysts for the Electrocatalytic Reduction of Nitrogen to Ammonia under Ambient Conditions

Powered by renewable electricity, the electrochemical reduction of nitrogen to ammonia is proposed as a promising alternative to the energy‐ and capital‐intensive Haber–Bosch process, and has thus attracted much attention from the scientific community. However, this process suffers from low NH₃ yields and Faradaic efficiency. The development of more effective electrocatalysts is of vital importance for the practical applications of this reaction. Of the reported catalysts, single‐atom catalysts (SACs) show the significant advantages of efficient atom utilization and unsaturated coordination configurations, which offer great scope for optimizing their catalytic performance. Herein, progress in state‐of‐the‐art SACs applied in the electrocatalytic N₂ reduction reaction (NRR) is discussed, and the main advantages and challenges for developing more efficient electrocatalysts are also highlighted.     

Electrocatalytically Active Fe-(O-C2)4 Single-Atom Sites for Efficient Reduction of Nitrogen to Ammonia

Single-atom catalysts have demonstrated their superiority over other types of catalysts for various reactions. However, the reported nitrogen reduction reaction single-atom electrocatalysts for the nitrogen reduction reaction exclusively utilize metal–nitrogen or metal–carbon coordination configurations as catalytic active sites. Here, we report a Fe single-atom electrocatalyst supported on low-cost, nitrogen-free lignocellulose-derived carbon. The extended X-ray absorption fine structure spectra confirm that Fe atoms are anchored to the support via the Fe-(O-C₂)₄ coordination configuration. Density functional theory calculations identify Fe-(O-C₂)₄ as the active site for the nitrogen reduction reaction. An electrode consisting of the electrocatalyst loaded on carbon cloth can afford a NH₃ yield rate and faradaic efficiency of 32.1 μg h⁻¹ mg_cat.⁻¹ (5350 μg h⁻¹ mg_Fe⁻¹) and 29.3 %, respectively. An exceptional NH₃ yield rate of 307.7 μg h⁻¹ mg_cat.⁻¹ (51 283 μg h⁻¹ mg_Fe⁻¹) with a near record faradaic efficiency of 51.0 % can be achieved with the electrocatalyst immobilized on a glassy carbon electrode.     

双金属氮化物Co3W3N/CNTs纳米复合材料的制备及其室温常压氮还原性能

采用水热法并经氨气保护热处理制备了双过渡金属氮化物Co3W3N/CNTs复合材料,得到了价格低廉且拥有良好氮电化学还原性能(NRR)的催化剂。通过调节已经预氧化的CNTs与过渡金属氮化物前驱体CoWO4的比例以及氨气热处理温度,实现了Co3W3N在CNTs表面的均匀负载。扫描电子显微镜(SEM)及透射电子显微镜(TEM)测试结果显示该电化学活性纳米微粒均匀地分散于CNTs表面,表明经预氧化的CNTs由于表面富集了较多的活性基团,有利于双过渡金属氮化物的分散生长。热处理后CNTs表面的Co3W3N微粒尺寸约为20 nm,相较于无载体的Co3W3N尺寸(100 nm)有明显减小。室温条件下,在N2饱和的0.01 mol·L^-1 H2SO4溶液中测试了该纳米复合材料在不同过电位下的NRR,该材料在-0.3 V(vs RHE)时的产氨率及法拉第效率分别可达12.73μg·h^-1·cm-2和13.59%,对比同样条件下,纯相Co3W3N的产氨率及法拉第效率仅为1.08μg·h^-1·cm^-2和1.76%。结果表明,通过水热反应和氨气保护热处理的Co3W3N/CNTs纳米复合材料具有良好的NRR性能。     

Catholyte‐Free Electrocatalytic CO2 Reduction to Formate

Electrochemical reduction of carbon dioxide (CO₂) into value‐added chemicals is a promising strategy to reduce CO₂ emission and mitigate climate change. One of the most serious problems in electrocatalytic CO₂ reduction (CO₂R) is the low solubility of CO₂ in an aqueous electrolyte, which significantly limits the cathodic reaction rate. This paper proposes a facile method of catholyte‐free electrocatalytic CO₂ reduction to avoid the solubility limitation using commercial tin nanoparticles as a cathode catalyst. Interestingly, as the reaction temperature rises from 303 K to 363 K, the partial current density (PCD) of formate improves more than two times with 52.9 mA cm^?2, despite the decrease in CO₂ solubility. Furthermore, a significantly high formate concentration of 41.5 g L^?1 is obtained as a one‐path product at 343 K with high PCD (51.7 mA cm^?2) and high Faradaic efficiency (93.3 %) via continuous operation in a full flow cell at a low cell voltage of 2.2 V.     

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

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

Electrocatalytic CO2 Reduction: from Discrete Molecular Catalysts to Their Integrated Catalytic Materials

Molecular catalysts (metal complexes), with molecularly defined uniform active sites and atomically precise structural tailorability allowing for regulating catalytic performance through metal- and ligand-centered engineering and elucidating reaction mechanisms via routine photoelectrochemical characterizations, have been increasingly explored for electrocatalytic CO₂ reduction (ECR). However, their poor stability and low catalytic current density are undesirable for practical applications. Heterogenizing discrete molecular catalysts can potentially surmount these issues, and the resulting integrated catalysts largely share catalytical properties with their discrete molecular counterparts, which bridge the gap between heterogeneous and homogeneous catalysis and combine their advantages. This minireview surveys advances in design and regulation of molecular catalysts such as porphyrin, phthalocyanine, and bipyridine-based metal complexes and their integrated catalytic materials for selective ECR.     

Ag/TiO2光催化还原硝酸氮

利用化学还原法制备不同Ag掺杂量TiO₂纳米催化剂,采用TEM、XRD、XRF和UV-Vis对催化剂进行表征。考察了催化剂在紫外光(254 nm)和可见光照射下还原初始浓度100 mgN·L^-1水相硝酸氮的活性和效果。重点考察了紫外光照射下Ag掺杂量、不同空穴捕获剂(甲酸、甲醇、乙酸、乙醇、草酸、草酸钠等)及甲酸浓度对硝酸氮还原的影响;对硝酸氮转化率和总氮去除率、形成亚硝酸氮、氨氮浓度及氮气选择性的影响。甲酸浓度为0.030 mol·L^-1、Ag掺杂量为1.0wt%时催化剂效果最佳。此时,硝酸氮、总氮的转化率分别为98.43%、78.13%;亚硝酸氮浓度为零,转化的硝酸氮中只有20.76%转化为氨氮,氮气选择性为79.24%。可见光下进行光催化还原反应时,硝酸氮转化率仅37.98%,但氮气的选择性较高。     

Electrocatalytically Active Fe‐(O‐C2)4 Single‐Atom Sites for Efficient Reduction of Nitrogen to Ammonia

Single‐atom catalysts have demonstrated their superiority over other types of catalysts for various reactions. However, the reported nitrogen reduction reaction single‐atom electrocatalysts for the nitrogen reduction reaction exclusively utilize metal–nitrogen or metal–carbon coordination configurations as catalytic active sites. Here, we report a Fe single‐atom electrocatalyst supported on low‐cost, nitrogen‐free lignocellulose‐derived carbon. The extended X‐ray absorption fine structure spectra confirm that Fe atoms are anchored to the support via the Fe‐(O‐C₂)₄ coordination configuration. Density functional theory calculations identify Fe‐(O‐C₂)₄ as the active site for the nitrogen reduction reaction. An electrode consisting of the electrocatalyst loaded on carbon cloth can afford a NH₃ yield rate and faradaic efficiency of 32.1 μg h^?1 mg_cat.^?1 (5350 μg h^?1 mg_Fe^?1) and 29.3 %, respectively. An exceptional NH₃ yield rate of 307.7 μg h^?1 mg_cat.^?1 (51 283 μg h^?1 mg_Fe^?1) with a near record faradaic efficiency of 51.0 % can be achieved with the electrocatalyst immobilized on a glassy carbon electrode.     

Recent Advances in Noble‐Metal‐Free Catalysts for Electrocatalytic Synthesis of Ammonia under Ambient Conditions

Ammonia is an essential chemical for producing fertilizers and energy carriers. However, the industrial Haber–Bosch process causes huge CO₂ emissions and energy waste. As a promising alternative for Haber‐Bosch process, electrochemical synthesis of ammonia has drawn much attention. Catalysts, as a vital part of electrochemical nitrogen reduction reaction (NRR), have developed rapidly in recent years. Compared to noble‐metal catalysts, noble‐metal‐free catalysts possess a low‐cost advantage. In this review, noble‐metal‐free catalysts, including metal‐based materials, metal organic frameworks (MOFs), MXenes, and metal‐free materials, are summarized. In addition, effective design strategies are discussed, along with the main problems and some potential directions of noble‐metal‐free NRR catalysts.     

Unveiling the Activity Origin of a Copper‐based Electrocatalyst for Selective Nitrate Reduction to Ammonia

Unveiling the active phase of catalytic materials under reaction conditions is important for the construction of efficient electrocatalysts for selective nitrate reduction to ammonia. The origin of the prominent activity enhancement for CuO (Faradaic efficiency: 95.8 %, Selectivity: 81.2 %) toward selective nitrate electroreduction to ammonia was probed. ¹⁵N isotope labeling experiments showed that ammonia originated from nitrate reduction. ¹H NMR spectroscopy and colorimetric methods were performed to quantify ammonia. In situ Raman and ex situ experiments revealed that CuO was electrochemically converted into Cu/Cu₂O, which serves as an active phase. The combined results of online differential electrochemical mass spectrometry (DEMS) and DFT calculations demonstrated that the electron transfer from Cu₂O to Cu at the interface could facilitate the formation of *NOH intermediate and suppress the hydrogen evolution reaction, leading to high selectivity and Faradaic efficiency.     

Electrocatalytic Reduction of CO2 to Acetic Acid by a Molecular Manganese Corrole Complex

The controlled electrochemical reduction of carbon dioxide to value added chemicals is an important strategy in terms of renewable energy technologies. Therefore, the development of efficient and stable catalysts in an aqueous environment is of great importance. In this context, we focused on synthesizing and studying a molecular Mn^III‐corrole complex, which is modified on the three meso‐positions with polyethylene glycol moieties for direct and selective production of acetic acid from CO₂. Electrochemical reduction of Mn^III leads to an electroactive Mn^II species, which binds CO₂ and stabilizes the reduced intermediates. This catalyst allows to electrochemically reduce CO₂ to acetic acid in a moderate acidic aqueous medium (pH 6) with a selectivity of 63 % and a turn over frequency (TOF) of 8.25 h^?1, when immobilized on a carbon paper (CP) electrode. In terms of high selectivity towards acetate, we propose the formation and reduction of an oxalate type intermediate, stabilized at the Mn^III‐corrole center.     

Defect Engineering Metal‐Free Polymeric Carbon Nitride Electrocatalyst for Effective Nitrogen Fixation under Ambient Conditions

Electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions provides an intriguing picture for the conversion of N₂ into NH₃. However, electrocatalytic NRR mainly relies on metal‐based catalysts, and it remains a grand challenge in enabling effective N₂ activation on metal‐free catalysts. Here we report a defect engineering strategy to realize effective NRR performance (NH₃ yield: 8.09 μg h^?1 mg^?1_cat., Faradaic efficiency: 11.59 %) on metal‐free polymeric carbon nitride (PCN) catalyst. Illustrated by density functional theory calculations, dinitrogen molecule can be chemisorbed on as‐engineered nitrogen vacancies of PCN through constructing a dinuclear end‐on bound structure for spatial electron transfer. Furthermore, the N?N bond length of adsorbed N₂ increases dramatically, which corresponds to “strong activation” system to reduce N₂ into NH₃. This work also highlights the significance of defect engineering for improving electrocatalysts with weak N₂ adsorption and activation ability.