Monodispersed Molecular Phthalocyanine with Sulfur-Driven Electron Delocalization for Enhanced Electrochemical Biosensing.

Heterogenizing the molecular catalysts on conductive scaffolds to achieve the isolated molecular dispersion and expected coordination structures is significant yet still challenging. Herein, a sulfur-driving strategy to anchor monodispersed cobalt phthalocyanine on nitrogen and sulfur co-doped graphene (NSG-CoPc) is demonstrated. Experimental and theoretical analysis prove that the incorporation of S dramatically improves the adsorption capability of NSG and evokes the monodispersion of the CoPc molecule, promoting the axial Co─N coordination and the electron delocalization of the Co catalytic center. Benefiting from the reduced activation energy barrier and boosted electron transfer, as well as the maximized active site utilization, NSG-CoPc exhibits outstanding H2O2 oxidization and sensing performance (used as a representative reaction). Moreover, the usage of NSG as a substrate can be readily extended to other metal (Ni, Cu, and Fe) phthalocyanine molecules with molecular-level dispersion. This work clarifies the mechanism of heteroatoms decoration and provides a new paradigm in devising monodispersed molecular catalysts with modulated chemical surroundings for broad applications.

Doping Regulation Stabilizing δ-MnO2 Cathode for High-Performance Aqueous Aluminium-ion Batteries.

δ-MnO2 is a promising cathode material for aqueous aluminium-ion batteries (AAIBs) for its layered crystalline structure with large interlayer spacing. However, the excellent Al ion storage performance of δ-MnO2 cathode remains elusive due to the frustrating structural collapse during the intercalation of high ionic potential Al ion species. Here, it is discovered that introducing heterogeneous metal dopants with high bond dissociation energy when bonded to oxygen can significantly reinforce the structural stability of δ-MnO2 frameworks. This reinforcement translates to stable cycling properties and high specific capacity in AAIBs. Vanadium-doped δ-MnO2 (V-δ-MnO2) can deliver a high specific capacity of 518 mAh g-1 at 200 mA g-1 with remarkable cycling stability for 400 cycles and improved rate capabilities (468, 339, and 285 mAh g-1 at 0.5, 1, and 2 A g-1, respectively), outperforming other doped δ-MnO2 materials and the reported AAIB cathodes. Theoretical and experimental studies indicate that V doping can substantially improve the cohesive energy of δ-MnO2 lattices, enhance their interaction with Al ion species, and increase electrical conductivity, collectively contributing to high ion storage performance. These findings provide inspiration for the development of high-performance cathodes for battery applications.

Synergistic Effect of P and Co Dual Doping Endows CuNi with High-Performance Hydrogen Evolution Reaction.

The rational design of highly active and durable non-noble electrocatalysts for hydrogen evolution reaction (HER) is significantly important but technically challenging. Herein, a phosphor and cobalt dual doped copper-nickel alloy (P, Co-CuNi) electrocatalyst with high-efficient HER performance is prepared by one-step electrodeposition method and reported for the first time. As a result, P, Co-CuNi only requires an ultralow overpotential of 56 mV to drive the current density of 10 mA cm-2, with remarkable stability for over 360 h, surpassing most previously reported transition metal-based materials. It is discovered that the P doping can simultaneously increase the electrical conductivity and enhance the corrosion resistance, while the introduction of Co can precisely modulate the sub-nanosheets morphology to expose more accessible active sites. Moreover, XPS, UPS, and DFT calculations reveal that the synergistic effect of different dopants can achieve the most optimal electronic structure around Cu and Ni, causing a down-shifted d-band center, which reduces the hydrogen desorption free energy of the rate-determining step (H2O + e- + H* → H2 + OH-) and consequently enhances the intrinsic activity. This work provides a new cognition toward the development of excellent activity and stability HER electrocatalysts and spurs future study for other NiCu-based alloy materials.

ICP-MS As a Contributing Tool to Nontarget Screening (NTS) Analysis for Environmental Monitoring.

Due to the increasing number of chemicals released into the environment, nontarget screening (NTS) analysis is a necessary tool for providing comprehensive chemical analysis of environmental pollutants. However, NTS workflows encounter challenges in detecting both known and unknown pollutants with common chromatography high-resolution mass spectrometry (HRMS) methods. Identification of unknowns is hindered by limited elemental composition information, and quantification without identical reference standards is prone to errors. To address these issues, we propose the use of inductively coupled plasma mass spectrometry (ICP-MS) as an element-specific detector. ICP-MS can enhance the confidence of compound identification and improve quantification in NTS due to its element-specific response and unambiguous chemical composition information. Additionally, mass balance calculations for individual elements (F, Br, Cl, etc.) enable assessment of total recovery of those elements and evaluation of NTS workflows. Despite its benefits, implementing ICP-MS in NTS analysis and environmental regulation requires overcoming certain shortcomings and challenges, which are discussed herein.

Green Synthesis of Carbon Nanodots (CNDs) Moderated by Flavonoid Extracts from Moringa oleifera Leaves and Co-Doped Sulfur/Nitrogen (NS - CNDs - Fla) and Their Potential for Heavy Metals Sensing Application.

Carbon nano dots (CNDs) has received a lot of attention in recent years due to their potential use in various kinds of applications. Many conventional chemical methods have been used to synthesis CNDs, but these processes have several drawbacks, such as hazardous by products, harsh chemicals, and high costs. To overcome these issues, green chemistry has an importance in the development of CNDs. Thus, it is essential to explore green synthesis approaches for production the CNDs. In this context, a novel precursor using flavonoid extraction from Moringa oleifera leaves is proposed. Moringa oleifera is the "magic tree" which contains many bioactive compounds such as flavonoids, especially in its leaves. Natural flavonoids and glycosides with specific components of structure can bind to metal ions. The content of bioactive compounds such as total flavonoids found in Moringa oleifera leaves is 172.10 mg/g. In addition, carbon (47.34%), nitrogen (51.67%), and sulfur (0.99%) are also the main composition. Then, the carbon nanodots (CNDs) synthesized in this research were moderated by flavonoid extract from Moringa oleifera using the hydrothermal method. The technique is easy, ecologically friendly, and requires neither specialized device or reagents. In practice, the CNDs produced are almost circular, with an average diameter of 3.49 nm. Furthermore, we enhanced synthesis CNDs - Fla with heteroatoms of nitrogen (N) and sulfur (S). They display a broad excitation-emission spectrum, excitation-dependent emission, and extraordinary fluorescence. Therefore, the synthesis of CNDs using flavonoids from Moringa oleifera as precursors would be a great potential candidate for the development of novel types of heavy metals sensing.

Non-Alternant Nanographenes Bearing N-Doped Non-Hexagonal Pairs: Synthesis, Structural Analysis and Photophysical Properties.

Introduction of non-hexagons and/or heteroatoms allows for finely tuning the physicochemical properties of nanographenes. Heteroatoms doping have dominated the modulation of nanographenes with tunable band gap, rich electrochemical activities and so on. The pair of non-hexagons, for instance, pentagon-heptagon pairs, have furnished nanographenes with aromatic and/or antiaromatic characteristics, open-shell properties and so on. In order to meet the growing demand for versatile nanographenes in materials science, research on novel nanographenes with heteroatom doped non-hexagonal pairs has been aroused in recent years. In this review, we focus on nanographenes with nitrogen-doped non-hexagonal paris including the synthesis, structure analysis, photophysical properties, and potential applications in organic devices.

Structural Design Induced Electronic Optimization in Single-Phase MoCoP Nanocrystal for Boosting Oxygen Reduction, Oxygen Evolution, and Hydrogen Evolution.

Structural and compositional design of multifunctional materials is critical for electrocatalysis, but their rational modulation and effective synthesis remain a challenge. Herein, a controllable one-pot synthesis for construction of trifunctional sites and preparation of porous structures is adopted for synthesizing dispersed MoCoP sites on N, P codoped carbonized substance. This tunable synthetic strategy also endorses the exploration of the electrochemical activities of Mo (Co)-based unitary, Mo/Co-based dual and MoCo-based binary metallic sites. Eventually benefiting from the structural regulation, MoCoP-NPC shows excellent oxygen reduction abilities with a half-wave potential of 0.880 V, and outstanding oxygen evolution and hydrogen evolution performance with an overpotential of 316 mV and 91 mV, respectively. MoCoP-NPC-based Zn-air battery achieves excellent cycle stability for 300 h and a high open-circuit voltage of 1.50 V. When assembled in a water-splitting device, MoCoP-NPC reaches 10 mA cm-2 at 1.65 V. Theoretical calculations demonstrate that the Co atom in the single-phase MoCoP has a low energy barrier for oxygen evolution reaction (OER) owing to the migration of Co 3d orbital toward the Fermi level. This work shows a simplified method for controllable preparation of prominent trifunctional catalysts.

Strain-Sensitive On-Surface Ladderization by Non-Dehydrogenative Heterocyclization.

On-surface cyclodehydrogenation recently became an important reaction to planarize π-conjugated molecules and oligomers. However, the high-activation barrier to cleave the C-H bond often requires high-temperature annealing, consequently restricting structures of precursor molecules and/or leading to random fusion at their edges. Here, we present a synthesis of pyrrolopyrrole-bridged ladder oligomers from 11,11,12,12-tetrabromo-1,4,5,8-tetraaza-9,10-anthraquinodimethane molecules on Ag(111) with bond-resolved scanning tunnelling microscopy. This non-dehydrogenative cyclization between pyrazine and ethynylene/cumulene groups has a low-activation barrier for forming intermediary dimeric oligomer containing dipyrazinopyrrolopyrrolopyrazine units, thus giving new insight into the strain-sensitive in ladder-oligomer formation.

Enhanced conversion of superoxide radical to singlet oxygen in peroxymonosulfate activation by metal-organic frameworks derived heteroatoms dual-doped porous carbon catalyst.

The activation of persulfate technology using carbon-based materials doped with heteroatoms has been extensively researched for the elimination of refractory pollutants in wastewater. In this study, metal-organic frameworks were utilized as precursors to synthesize P, N dual-doped carbon material (PNC), which was employed to activate peroxymonosulfate (PMS) for the degradation of tetracycline hydrochloride (TCH). The results demonstrated a 90.2% removal efficiency of total organic carbon within 60 min. The significant increase of surface defects on the nitrogen self-doped porous carbon materials anchored with phosphorus promoted the conversion of superoxide radical to singlet oxygen during PMS activation, which was identified as the key active species of PNC/PMS system. Additionally, the enhanced direct electron transfer also facilitated the degradation of TCH. Consequently, TCH was successfully degraded into nontoxic and harmless inorganic small molecules. The findings of this research provide valuable insights into improving the performance of heteroatom-doped carbon materials for pollutant degradation by activating PMS and transforming the non-radical pathway. The results highlight the potential of metal-organic frameworks derived heteroatoms dual-doped porous carbon catalysts for the development of advanced treatment technologies in wastewater treatment.

Nitrogen and sulfur co-doped porous carbon derived from polypyrrole-polythiophene for efficient peroxydisulfate activation towards degradation of aniline.

To enhance the catalytic activity of carbon materials and streamline their synthesis process, it is necessary to optimize the doping of heteroatoms and reduce the dependence on organic solvents. This can be achieved by utilizing carbonized Polypyrrole-Polythiophene (C(Ppy-Pth)), which is obtained through simultaneous and in-situ co-doping of N and S. This material can serve as an effective activator of peroxydisulfate (PDS) for the degradation of aniline (AN). The results showed that Ppy-Pth could be efficiently synthesized by using cetyltrimethyl ammonium bromide, pyrrole, thiophene, FeCl3, and H2O2 in water. Based on the price, self-decomposition and oxidation efficiency, the performance of PDS activated by C(Ppy-Pth) was superior to that of peroxymonosulfate (PMS) in degrading AN. The optimum conditions for catalyzing PDS and degrading 30 mg/L AN by C(Ppy-Pth) were 0.10 g/L C(Ppy-Pth)-1000-1/1, 2.10 mM PDS, and pH0 = 3.00, which resulted in 86.69% AN removal in 30 min. Carbonation temperature, N/S ratio and pyridine N content are the key factors affecting the catalytic activity of C(Ppy-Pth). Quenching, probe, and electrochemical experiment revealed that in the catalytic PDS system with C(Ppy-Pth)-1000-1/1 (pH0 = 3.00), the oxidation of AN mainly occurred through the generation of hydroxyl radical (·OH), superoxide anion (O2·-), and electron transfer on the C(Ppy-Pth)-1000-1/1 surface. The steady-state concentration of ·OH and O2·- were 2.65 × 10-14 M and 1.97 × 10-13 M, respectively, and the contribution rate of ·OH oxidation was 31.28%. The oxidation of AN by sulfate radical (SO4·-) and singlet oxygen (1O2) could be neglected. This study provides a promising strategy for the construction of PDS catalyst and wastewater treatment.

Metal-Free One-Pot Multi-Functionalization of Unsaturated Compounds with Interelement Compounds by Radical Process.

In recent years, the importance of "environmentally friendly manufacturing" has been increasing toward the establishment of a resource-recycling society. In organic synthesis, as well, it is becoming increasingly important to develop new synthetic strategies with resource conservation and the recycling of elemental resources in mind, rather than just only synthesis. Many studies on the construction of frameworks of functional molecules using ionic reactions and transition-metal-catalyzed reactions have been reported, but most of them have focused on the formation of carbon-carbon bonds. However, it is essential to introduce appropriate functional groups at appropriate positions in molecules in order for the molecules to express their functions, and furthermore, the highly selective preparation of multiple functional groups is considered important for the creation of new functional molecules. In this review, we focus on radical reactions with high functional group selectivity and overview the recent progress in practical methods for the simultaneous introduction of multiple functional groups and propose future synthetic strategies that emphasize the recycling of elemental resources and environmental friendliness.

Recent Advances in the Synthesis of Di- and Trisubstituted Hydroxylamines.

As an underrepresented functional group in bioorganic and medicinal chemistry, the hydroxylamine unit has historically received little attention from the synthetic community. Recent developments, however, suggest that hydroxylamines may have broader applications such that a review covering recent developments in the synthesis of this functional group is timely. With this in mind, this review primarily covers developments in the past 15 years in the preparation of di- and trisubstituted hydroxylamines. The mechanism of the reactions and key features and shortcomings are discussed throughout the review.

Recent Advances and Synergistic Effects of Non-Precious Carbon-Based Nanomaterials as ORR Electrocatalysts: A Review.

The use of platinum-free (Pt) cathode electrocatalysts for oxygen reduction reactions (ORRs) has been significantly studied over the past decade, improving slow reaction mechanisms. For many significant energy conversion and storage technologies, including fuel cells and metal-air batteries, the ORR is a crucial process. These have motivated the development of highly active and long-lasting platinum-free electrocatalysts, which cost less than proton exchange membrane fuel cells (PEMFCs). Researchers have identified a novel, non-precious carbon-based electrocatalyst material as the most effective substitute for platinum (Pt) electrocatalysts. Rich sources, outstanding electrical conductivity, adaptable molecular structures, and environmental compatibility are just a few of its benefits. Additionally, the increased surface area and the simplicity of regulating its structure can significantly improve the electrocatalyst's reactive sites and mass transport. Other benefits include the use of heteroatoms and single or multiple metal atoms, which are capable of acting as extremely effective ORR electrocatalysts. The rapid innovations in non-precious carbon-based nanomaterials in the ORR electrocatalyst field are the main topics of this review. As a result, this review provides an overview of the basic ORR reaction and the mechanism of the active sites in non-precious carbon-based electrocatalysts. Further analysis of the development, performance, and evaluation of these systems is provided in more detail. Furthermore, the significance of doping is highlighted and discussed, which shows how researchers can enhance the properties of electrocatalysts. Finally, this review discusses the existing challenges and expectations for the development of highly efficient and inexpensive electrocatalysts that are linked to crucial technologies in this expanding field.

In Situ Filling of the Oxygen Vacancies with Dual Heteroatoms in Co3O4 for Efficient Overall Water Splitting.

Electrocatalytic water splitting is a crucial area in sustainable energy development, and the development of highly efficient bifunctional catalysts that exhibit activity toward both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of paramount importance. Co3O4 is a promising candidate catalyst, owing to the variable valence of Co, which can be exploited to enhance the bifunctional catalytic activity of HER and OER through rational adjustments of the electronic structure of Co atoms. In this study, we employed a plasma-etching strategy in combination with an in situ filling of heteroatoms to etch the surface of Co3O4, creating abundant oxygen vacancies, while simultaneously filling them with nitrogen and sulfur heteroatoms. The resulting N/S-VO-Co3O4 exhibited favorable bifunctional activity for alkaline electrocatalytic water splitting, with significantly enhanced HER and OER catalytic activity compared to pristine Co3O4. In an alkaline overall water-splitting simulated electrolytic cell, N/S-VO-Co3O4 || N/S-VO-Co3O4 showed excellent overall water splitting catalytic activity, comparable to noble metal benchmark catalysts Pt/C || IrO2, and demonstrated superior long-term catalytic stability. Additionally, the combination of in situ Raman spectroscopy with other ex situ characterizations provided further insight into the reasons behind the enhanced catalyst performance achieved through the in situ incorporation of N and S heteroatoms. This study presents a facile strategy for fabricating highly efficient cobalt-based spinel electrocatalysts incorporated with double heteroatoms for alkaline electrocatalytic monolithic water splitting.

Sodium Storage Properties of Carbonaceous Flowers.

As a promising energy storage system, sodium-ion batteries face challenges related to the stability and high-rate capability of their electrode materials, especially carbon, which is the most studied anode. Previous studies have demonstrated that three-dimensional architectures composed of porous carbon materials with high electrical conductivity have the potential to enhance the storage performance of sodium-ion batteries. Here, high-level N/O heteroatoms-doped carbonaceous flowers with hierarchical pore architecture are synthesized through the direct pyrolysis of homemade bipyridine-coordinated polymers. The carbonaceous flowers could provide effective transport pathways for electrons/ions, thus allowing for extraordinary storage properties in sodium-ion batteries. As a consequence, sodium-ion battery anodes made of carbonaceous flowers exhibit outstanding electrochemical features, such as high reversible capacity (329 mAh g-1 at 30 mA g-1), superior rate capability (94 mAh g-1 at 5000 mA g-1), and ultralong cycle lifetimes (capacity retention rate of 89.4% after 1300 cycles at 200 mA g-1). To better investigate the sodium insertion/extraction-related electrochemical processes, the cycled anodes are experimentally analyzed with scanning electron microscopy and transmission electron microscopy. The feasibility of the carbonaceous flowers as anode materials was further investigated using a commercial Na3V2(PO4)3 cathode for sodium-ion full batteries. All these findings indicate that carbonaceous flowers may possess great potential as advanced materials for next-generation energy storage applications.

Fluorine Engineered Self-Supported Ultrathin 2D Nickel Hydroxide Nanosheets as Highly Robust and Stable Bifunctional Electrocatalysts for Oxygen Evolution and Urea Oxidation Reactions.

Developing highly efficient noble-metal-free electrocatalysts with a scalable and environmentally friendly synthesis approach remains a challenge in the field of electrocatalytic water splitting. To overcome this problem, self-supported fluorine-modified 2D ultrathin nickel hydroxide (F-Ni(OH)2 ) nanosheets (NSs) for the oxygen evolution reaction (OER) and urea oxidation reaction (UOR) are prepared with a scalable and ascendant one-step synthesis route. The enhanced redox activity, electrical conductivity and a great number of exposed active sites of the heterogeneous catalysts improve charge migration for the electrocatalytic reactions. The density of states of the d orbitals of the Ni atoms significantly increases near the Fermi level, thereby indicating that the Ni atoms near the F-dopants promote electrical conduction in the Ni(OH)2 monolayer. The F-Ni(OH)2 electrocatalyst exhibits notable OER and UOR activity with onset potentials of 1.43 and 1.16 V versus RHE, respectively required to reach 10 mA cm-2 , which are comparable to those of commercial noble-metal-based electrocatalysts. With RuCo-OH nanospheres, the settled F-Ni(OH)2 ||RuCo-OH cell requires merely 1.55 and 1.37 V to reach 10 mA cm-2 with superb durability for 24 h in overall water and urea electrolysis, respectively. Overall, high-quality, and efficient noble-metal-free electrocatalysts for overall water and urea electrolysis can be prepared with a simple, scalable, and reproducible preparation method.

N, S-Coordinated Co Single Atomic Catalyst Boosting Adsorption and Conversion of Lithium Polysulfides for Lithium-Sulfur Batteries.

Boosting reversible solid-liquid phase transformation from lithium polysulfides to Li2 S and suppressing the shuttling of lithium polysulfides from the cathode to the lithium anode are critical challenges in lithium-sulfur batteries. Here, sulfiphilic single atomic cobalt implanted in lithiophilic heteroatoms-dopped carbon (SACo@HC) matrix with a CoN3 S structure for high-performance lithium-sulfur batteries is reported. Density functional theory calculation and in situ experiments demonstrate that the optimal CoN3 S structure in SACo@HC can effectively improve the adsorption and redox conversion efficiency of lithium polysulfides. Consequently, the S-SACo@HC composite with sulfur loading of 80 wt% delivers a high capacity of 1425.1 mAh g-1 at 0.05 C and outstanding rate performance with 745.9 mAh g-1 at 4 C. Furthermore, a capacity of 680.8 mAh g-1 at 0.5 C with a low electrolyte/sulfur ratio (6 µL mg-1 ) can be achieved even after 300 cycles. With the harsh conditions of lean electrolyte (E/S = 4 µL mg-1 ) and high sulfur loading (5.4 mg cm-2 ), a superior area capacity of 5.8 mAh cm-2 can be obtained. This work contributes to building a profound understanding of the adsorption and interface engineering of lithium polysulfides and provides ideas to tackle the long-standing polysulfide shuttle problem of lithium-sulfur batteries.

Phase-Controlled Synthesis of Nickel-Iron Nitride Nanocrystals Armored with Amorphous N-Doped Carbon Nanoparticles Nanocubes for Enhanced Overall Water Splitting.

Transition metal nitrides (TMNs) nanostructures possess distinctive electronic, optical, and catalytic properties, showing great promise to apply in clean energy, optoelectronics, and catalysis fields. Nonetheless, phase-regulation of NiFe-bimetallic nitrides nanocrystals or nanohybrid architectures confronts challenges and their electrocatalytic overall water splitting (OWS) performances are underexplored. Herein, novel pure-phase Ni2+ x Fe2- x N nanocrystals armored with amorphous N-doped carbon (NC) nanoparticles nanocubes (NPNCs) are obtained by controllable nitridation of NiFe-Prussian-blue analogues derived oxides/NC NPNCs under Ar/NH3 atmosphere. Such Ni2+ x Fe2- x N/NC NPNCs possess mesoporous structures and show enhanced electrocatalytic activity in 1 m KOH electrolyte with the overpotential of 101 and 270 mV to attain 10 and 50 mA cm-2 current toward hydrogen and oxygen evolution reactions, outperforming their counterparts (mixed-phase NiFe2 O4 /Ni3 FeN/NC and NiFe oxides/NC NPNCs). Remarkably, utilizing them as bifunctional catalysts, the assembled Ni2+ x Fe2- x N/NC||Ni2+ x Fe2- x N/NC electrolyzer only needs 1.51 V cell voltage for driving OWS to approach 10 mA cm-2 water-splitting current, exceeding their counterparts and the-state-of-art reported bifunctional catalysts-based devices, and Pt/C||IrO2 couples. Additionally, the Ni2+ x Fe2- x N/NC||Ni2+ x Fe2- x N/NC manifests excellent durability for OWS. The findings presented here may spur the development of advanced TMNs nanostructures by combining phase, structure engineering, and hybridization strategies and stimulate their applications toward OWS or other clean energy fields.

General Design Strategy of Anti-aromatic Porphyrinoids.

A systematic investigation to arrange the typical anti-aromatic porphyrinoids in sequence was performed. Based on density functional theory calculations, six rules are summarized to obtain the high-performance anti-aromatic porphyrinoids: (1) when two atoms are deleted/added on the 18π electron current ring flowing pipe, we will immediately obtain a 16π/20π electron anti-aromatic system; (2) it is a good idea to increase the number of pyrrole/thiophen/furan units on the π-electron current ring flowing pipe; (3) the heteroatom selecting order is -O- (optimal choice), -NH- (second choice), and -S- (last choice); (4) it is worth noting that the C-C=C-C unit is not beneficial for the anti-aromatic properties; (5) it is very significant to avoid the crowded environment in the core space of an anti-aromatic molecule. In this view, -O- is much better than -S- and -NH-; (6) the "circular" skeleton is much better than an "ellipse-like", "rectangular", or "parallelogram-like" one.

Heteroatoms Induce Localization of the Electric Field and Promote a Wide Potential-Window Selectivity Towards CO in the CO2 Electroreduction.

Carbon dioxide electroreduction (CO2 RR) is a sustainable way of producing carbon-neutral fuels. Product selectivity in CO2 RR is regulated by the adsorption energy of reaction-intermediates. Here, we employ differential phase contrast-scanning transmission electron microscopy (DPC-STEM) to demonstrate that Sn heteroatoms on a Ag catalyst generate very strong and atomically localized electric fields. In situ attenuated total reflection infrared spectroscopy (ATR-IR) results verified that the localized electric field enhances the adsorption of *COOH, thus favoring the production of CO during CO2 RR. The Ag/Sn catalyst exhibits an approximately 100 % CO selectivity at a very wide range of potentials (from -0.5 to -1.1 V, versus reversible hydrogen electrode), and with a remarkably high energy efficiency (EE) of 76.1 %.