Triadic Sites Drive Tandem CO2-to-Ethanol Conversion by Steering *CO Coverage and *COH Intermediate Formation
Fang Zhao1, Bo Huang1, Huayi Kuang2
1Key Laboratory of Cluster Science, Beijing Key Laboratory of Construction-Tailorable Advanced Functional Materials and Green Applications, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, China.
Angewandte Chemie (International Ed. in English)
|July 21, 2026
Summary
We engineered single copper-coordinated nitrogen-doped carbon (Cu1-NC) with a high pyrrolic-N to pyridinic-N ratio for efficient electrocatalytic CO2 reduction to ethanol. This novel catalyst design achieves high selectivity by optimizing reaction pathways.
Area of Science:
- Materials Science
- Electrochemistry
- Catalysis
Background:
- Single metal-coordinated nitrogen-doped carbon (M1-NC) materials are promising for CO2 reduction.
- Controlling nitrogen configurations in M1-NC is crucial for selective ethanol production.
- Current challenges include precisely modulating nitrogen sites to steer reaction pathways.
Purpose of the Study:
- To design and synthesize a novel Cu1-NC catalyst with a high pyrrolic-N to pyridinic-N ratio for enhanced electrocatalytic CO2 reduction to ethanol.
- To elucidate the synergistic roles of pyrrolic-N and pyridinic-N with single Cu sites in promoting ethanol selectivity.
- To investigate the general applicability of this strategy to other metal-based M1-NC catalysts.
Main Methods:
- Synthesis of Cu1-NC anchored on a carbon support with a high pyrrolic-N/pyridinic-N ratio (CuN4/pr-h-NC).
- Electrochemical characterization including Faradaic efficiency (FE) measurements for ethanol production.
- Density Functional Theory (DFT) calculations to understand reaction mechanisms and identify potential-determining steps (PDS).
Main Results:
- The designed CuN4/pr-h-NC catalyst achieved an exceptional FE of 79.6% for ethanol.
- Experimental and theoretical studies revealed synergistic triadic sites formed by pyrrolic-N, pyridinic-N, and Cu sites.
- The PDS shifted from C-C coupling to *CO protonation, facilitated by pyrrolic N boosting *CO coverage and subsequent hydrogenation at pyridinic N sites.
- The mechanism proved independent of the specific metal, with ZnN4/pr-h-NC showing 71.8% FE for ethanol.
Conclusions:
- A novel ensemble site engineering strategy using M1-NC materials with tailored nitrogen configurations can effectively steer CO2 electroreduction towards ethanol.
- The high pyrrolic-N to pyridinic-N ratio is key to optimizing the catalytic performance for ethanol production.
- This approach offers a promising pathway for developing highly selective and efficient electrocatalysts for CO2 conversion.
Related Concept Videos
01:12Arteries of the Upper Limbs
The subclavian artery transitions into the axillary artery as it exits the chest and enters the axillary region. This artery is critical for supplying blood to the shoulder area, including the head of the humerus, through the humeral circumflex arteries. As the vessel continues into the upper arm or brachium, it becomes the brachial artery. This artery plays a key role in vascularizing the brachial region and bifurcates at the elbow into several branches. These branches include the deep...
![[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2Ffiles%2Fmedia%2Fscience-education%2Fscience-education-thumbs%2F13097.jpg&w=3840&q=75)
01:24[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.
01:19Anastomoses
In human anatomy, anastomosis refers to a connection or opening between two things, particularly between blood vessels or other tubular structures. The term is derived from the Greek term 'anastomosis,' which means 'outlet' or 'opening.' This natural network of connections plays a critical role in the survival and functionality of the human body.
Anastomoses can be formed at arterial, venous, and lymphatic vessels.
Arterial Anastomosis: These occur between arteries. They are most common in...
Anastomoses can be formed at arterial, venous, and lymphatic vessels.
Arterial Anastomosis: These occur between arteries. They are most common in...
01:10The Arch of Aorta
The coronary arteries, originating from the ascending aorta, bifurcate from two sinuses located within the ascending aorta. Positioned just above the aortic semilunar valve, these sinuses house essential aortic baroreceptors and chemoreceptors, crucial for maintaining cardiac function. The left coronary artery and the right coronary artery branch off from the left posterior and anterior aortic sinuses, respectively.
Encircling the heart, the coronary arteries form a ring-like structure before...
Encircling the heart, the coronary arteries form a ring-like structure before...
01:09EDTA: Conditional Formation Constant
Each EDTA molecule has six binding sites: four carboxyl groups and two amino groups. The fully protonated form of EDTA is represented as H6Y2+. However, it can exist in different forms, H5Y+, H4Y, H3Y−, H2Y2−, and HY3−, depending on the pH of the solution. In very basic solutions with pH > 10.17, the fully deprotonated form, Y4−, is the predominant species that readily complexes with metal ions in a 1:1 ratio.
For the equilibrium reaction of the metal with the Y4− form of EDTA, the formation...
For the equilibrium reaction of the metal with the Y4− form of EDTA, the formation...
01:33Aldol Condensation vs Claisen Condensation
Aldol condensation is an acid or base-catalyzed condensation between aldehydes or ketones to give an α,ꞵ-unsaturated carbonyl compound. A base-promoted condensation between ester molecules to produce a ꞵ-ketoester is known as the Claisen condensation. In the presence of a base, both reactions involve deprotonation of the acidic α hydrogen to produce the corresponding enolates. The nucleophilic enolates attack their respective nonenolized carbonyl compound forming a tetrahedral intermediate.