Electrocatalytic CO2 reduction by heterogeneous molecular catalysts is emerging as an important area for CO2 utilization. Unlike commonly used solid heterogeneous catalysts, molecular catalysts possess well-defined structure, which allows the establishment of a precise structural model for better understanding of the CO2 reduction mechanism. The easy modification of molecular catalysts with designated functional fragments through organic synthesis skills also facilitates the development of novel and efficient molecular catalysts. The direct use of molecular catalysts in the homogeneous phase suffers from poor solubility in some common solvents, low utilization and difficulty in recycling. Heterogeneous immobilization of molecular catalysts onto a substrate can potentially solve these problems. This review summarizes the methods that have been developed so far for heterogeneous immobilization of homogeneous molecular catalysts, including covalent/non-covalent bonding, and assembling the molecular catalysts into a periodic skeleton. Challenges and factors affecting the activities of such catalysts in electrochemical CO2 reduction are also discussed.

Electrocatalytic reduction of carbon dioxide: opportunities with heterogeneous molecular catalysts

The electrochemical reduction of carbon dioxide (CO2) powered by renewable energy is an attractive sustainable approach to mitigate CO2 emissions and to produce fuels or value-added chemicals. In order to tackle the challenges related to selectivity, activity, overpotential and durability, transition metal-based catalysts have been widely investigated in the last decades. In an effort to bridge the gap between the fields of homogeneous and heterogeneous catalysis, this review aims to survey the main strategies explored for the rational design of a wide variety of different metal catalysts, ranging from molecular systems to single-atom and nanostructured catalysts. Transition metal complexes containing heme and non-heme ligands have been selected to discuss the recent advances in the understanding of the structure–function relationship in molecular homogeneous catalysis as well as to summarize the main approaches proposed for the heterogenization or confinement of molecular catalysts on conductive surfaces. The main strategies to minimize catalyst cost are also presented, leading to atomically dispersed molecular-like M–Nx moieties embedded on 2D conducting materials. The superior performances of single-atom catalysts (SACs) and the structural similarity with their molecular analogs, suggest that transition metal catalysts containing well-defined sites may be intrinsically more active and selective towards CO2 conversion than the bulk heterogeneous materials. Finally, design approaches for metal nanoparticles (NPs) based on size, shape, and support tuning are summarized and compared to novel strategies based on the interaction with surface-bonded organic molecules. The studies herein presented show that the basic principles in molecular catalysis and organometallic chemistry can be effectively used to design new efficient and selective heterogeneous catalysts for CO2 reduction.

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Transition metal-based catalysts for the electrochemical CO2 reduction: from atoms and molecules to nanostructured materials

Semiconductor photocatalysis is a promising technology to tackle refractory antibiotics contamination in water. Herein, a facile in situ growth strategy is developed to implant single-atom cobalt in polymeric carbon nitride (pCN) via the bidentate ligand for efficient photocatalytic degradation of oxytetracycline (OTC). The atomic characterizations indicate that single-atom cobalt is successfully anchored on pCN by covalently forming the CoO bond and CoN bond, which will strengthen the interaction between single-atom cobalt and pCN. This single-atom cobalt can efficiently expand optical absorption, increase electron density, facilitate charge separation and transfer, and promote OTC degradation. As the optimal sample, Co(1.28%)pCN presents an outstanding apparent rate constant for OTC degradation (0.038 min-1 ) under visible light irradiation, which is about 3.7 times than that of the pristine pCN. The electron spin resonance (ESR) tests and reactive species trapping experiments demonstrate that the 1 O2 , h+ , •O2 - , and •OH are responsible for OTC degradation. This work develops a new way to construct single-atom-modified pCN and provides a green and highly efficient strategy for refractory antibiotics removal.

In Situ Grown Single-Atom Cobalt on Polymeric Carbon Nitride with Bidentate Ligand for Efficient Photocatalytic Degradation of Refractory Antibiotics

Earth-abundant Fe, Ni, and Co aza macrocyclic and polypyridine complexes have been thoroughly investigated for CO2 electrochemical and visible-light-driven reduction. Since the first reports in the 1970s, an enormous body of work has been accumulated regarding the two-electron two-proton reduction of the gas, along with mechanistic and spectroscopic efforts to rationalize the reactivity and establish guidelines for structure-reactivity relationships. The ability to fine tune the ligand structure and the almost unlimited possibilities of designing new complexes have led to highly selective and efficient catalysts. Recent efforts toward developing hybrid systems upon combining molecular catalysts with conductive or semi-conductive materials have converged to high catalytic performances in water solutions, to the inclusion of these catalysts into CO2 electrolyzers and photo-electrochemical devices, and to the discovery of catalytic pathways beyond two electrons. Combined with the continuous mechanistic efforts and new developments for in situ and in operando spectroscopic studies, molecular catalysis of CO2 reduction remains a highly creative approach.

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Molecular catalysis of CO2 reduction: recent advances and perspectives in electrochemical and light-driven processes with selected Fe, Ni and Co aza macrocyclic and polypyridine complexes

Towards highly efficient electrochemical CO2 reduction: Cell designs, membranes and electrocatalysts

Electrochemical reduction of CO2 is promising to utilize the intermittent renewable electricity and transform CO2 into value-added products, simultaneously. Herein, we designed a cobalt phthalocyanine-based catalyst supported on pyridine-functionalized carbon nanotubes (CoPc-py-CNT). This novel hybrid catalyst exhibited a high activity (TOFCO: 34.5 s−1 at −0.63 V vs. RHE) and selectivity (FECO > 98%) for electrochemical CO2 reduction. To the best of our knowledge, it is the best one among all reported molecular based electrocatalysts for CO2-to-CO conversion. Furthermore, structure characterizations (such as Raman and X-rays photoelectron spectroscopy), loading-dependent electrochemical analysis and mechanistic studies revealed that pyridine groups, through axial coordination with Co, not only functioned as physical promoters to improve the dispersion of cobalt phthalocyanine but also tuned the electronic structure of Co sites to increase the intrinsic turnover frequency.

Xiangchen Fang

Papers

Cobalt phthalocyanine coordinated to pyridine-functionalized carbon nanotubes with enhanced CO2 electroreduction