Metal‐Free Carbon Materials for CO2 Electrochemical Reduction

The rapid increase of the CO₂ concentration in the Earth's atmosphere has resulted in numerous environmental issues, such as global warming, ocean acidification, melting of the polar ice, rising sea level, and extinction of species. To search for suitable and capable catalytic systems for CO₂ conversion, electrochemical reduction of CO₂ (CO₂RR) holds great promise. Emerging heterogeneous carbon materials have been considered as promising metal‐free electrocatalysts for the CO₂RR, owing to their abundant natural resources, tailorable porous structures, resistance to acids and bases, high‐temperature stability, and environmental friendliness. They exhibit remarkable CO₂RR properties, including catalytic activity, long durability, and high selectivity. Here, various carbon materials (e.g., carbon fibers, carbon nanotubes, graphene, diamond, nanoporous carbon, and graphene dots) with heteroatom doping (e.g., N, S, and B) that can be used as metal‐free catalysts for the CO₂RR are highlighted. Recent advances regarding the identification of active sites for the CO₂RR and the pathway of reduction of CO₂ to the final product are comprehensively reviewed. Additionally, the emerging challenges and some perspectives on the development of heteroatom‐doped carbon materials as metal‐free electrocatalysts for the CO₂RR are included.     

Efficient Metal‐Free Electrocatalysts from N‐Doped Carbon Nanomaterials: Mono‐Doping and Co‐Doping

N‐doped carbon nanomaterials have rapidly grown as the most important metal‐free catalysts in a wide range of chemical and electrochemical reactions. This current report summarizes the latest advances in N‐doped carbon electrocatalysts prepared by N mono‐doping and co‐doping with other heteroatoms. The structure–performance relationship of these materials is subsequently rationalized and perspectives on developing more efficient and sustainable electrocatalysts from carbon nanomaterials are also suggested.     

Carbon‐Based Metal‐Free Catalysts for Key Reactions Involved in Energy Conversion and Storage

Electrocatalysts are key for renewable energy technologies and other important industrial processes. Currently, noble metals and metal oxides are the most widely used catalysts for electrocatalysis. However, metal‐based catalysts often suffer from multiple disadvantages, including high cost, low selectivity, poor durability, impurity poisoning and fuel crossover effects, and detrimental effects on the environment. Therefore, carbon‐based metal‐free catalysts have received increasing interest as promising electrocatalysts for advanced energy conversion and storage. Recently, tremendous progress has been achieved in the development of low‐cost, efficient carbon‐based metal‐free catalysts for renewable energy technologies and beyond. Here, a concise, but comprehensive and critical, review of recent advances in the field of carbon‐based metal‐free catalysts is provided. A brief overview of various reactions involved in renewable energy conversion and storage, including the oxygen reduction reaction, hydrogen evolution reaction, oxygen evolution reaction, carbon dioxide reduction reaction, nitrogen reduction reaction, and bifunctional/multifunctional electrocatalysis, along with some challenges and opportunities, is presented.     

Sustainable Carbonaceous Materials Derived from Biomass as Metal‐Free Electrocatalysts

Although carbon is the second most abundant element in the biosphere, a large proportion of the available carbon resources in biomass from agriculture, stock farming, ocean fisheries, and other human activities is currently wasted. The use of sustainable carbonaceous materials as an alternative to precious metals in electrocatalysis is a promising pathway for transforming sustainable biomass resources into sustainable energy‐conversion systems. The development of rational syntheses of metal‐free carbonaceous catalysts derived from sustainable biomass has therefore become a topic of significant interest in materials chemistry. However, great efforts are still required to develop methods that are low cost, scalable, and environmentally friendly and which afford carbonaceous materials having an electrocatalytic performance comparable to, or even better than, existing precious metal catalysts. Herein, recent achievements in developing metal‐free carbonaceous catalysts based on biomass are reviewed and discussed and the critical issues which still need to be addressed are highlighted. The focus is on representative synthesis and optimization strategies applicable to different kinds of biomass, as well as studies of the physicochemical structure and electrochemical performance of the resulting metal‐free carbonaceous catalysts. Finally, some guidelines for the future development of this important area are provided.     

3D Heteroatom‐Doped Carbon Nanomaterials as Multifunctional Metal‐Free Catalysts for Integrated Energy Devices

Sustainable and cost‐effective energy generation has become crucial for fulfilling present energy requirements. For this purpose, the development of cheap, scalable, efficient, and reliable catalysts is essential. Carbon‐based heteroatom‐doped, 3D, and mesoporous electrodes are very promising as catalysts for electrochemical energy conversion and storage. Various carbon allotropes doped with a variety of heteroatoms can be utilized for cost‐effective mass production of electrode materials. 3D porous carbon electrodes provide multiple advantages, such as large surface area, maximized exposure to active sites, 3D conductive pathways for efficient electron transport, and porous channels to facilitate electrolyte diffusion. However, it is challenging to synthesize and functionalize isotropic 3D carbon structures. Here, various synthesis processes of 3D porous carbon materials are summarized to understand how their physical and chemical properties together with heteroatom doping dictate the electrochemical catalytic performance. Prospects of attractive 3D carbon structural materials for energy conversion and efficient integrated energy systems are also discussed.     

Carbon‐Based Metal‐Free Catalysts for Electrocatalytic Reduction of Nitrogen for Synthesis of Ammonia at Ambient Conditions

The electrocatalytic nitrogen reduction reaction (NRR) is a promising catalytic system for N₂ fixation in ambient conditions. Currently, metal‐based catalysts are the most widely studied catalysts for electrocatalytic NRR. Unfortunately, the low selectivity and poor resistance to acids and bases, and the low Faradaic efficiency, production rate, and stability of metal‐based catalysts for NRR make them uncompetitive for the synthesis of ammonia in comparison to the industrial Haber–Bosch process. Inspired by applications of carbon‐based metal‐free catalysts (CMFCs) for the oxygen reduction reaction (ORR) and CO₂ reduction reaction (CO₂RR), the studies of these CMFCs in electrocatalytic NRR have attracted great attention in the past year. However, due to the differences in electrocatalytic NRR, there are several critical issues that need to be addressed in order to achieve rational design of advanced carbon‐based metal‐free electrocatalysts to improve activity, selectivity, and stability for NRR. Herein, the recent developments in the field of carbon‐based metal‐free NRR catalysts are presented, along with critical issues, challenges, and perspectives concerning metal‐free catalysts for electrocatalytic reduction of nitrogen for synthesis of ammonia at ambient conditions.     

Recent Advances in Carbon‐Based Metal‐Free Electrocatalysts

Precious noble metals (such as Pt, Ir) and nonprecious transition metals (e.g., Fe, Co), including their compounds (e.g., oxides, nitrides), have been widely investigated as efficient catalysts for energy conversion, energy storage, important chemical productions, and many industrial processes. However, they often suffer from high cost, low selectivity, poor durability, and susceptibility to gas poisoning with adverse environmental issues. As a low‐cost alternative, the first carbon‐based metal‐free catalyst (C‐MFC based on N‐doped carbon nanotubes) was discovered in 2009. Since then, various C‐MFCs have been demonstrated to show similar or even better catalytic performance than their metal‐based counterparts, attractive energy conversion and storage (e.g., fuel cells, metal–air batteries, water splitting), environmental remediation, and chemical production. Enormous progress has been achieved while the number of publications still rapidly increases every year. Herein, a critical overview of the very recent advances in this rapidly developing field during the last couple of years is presented.     

Chemical Approaches to Carbon‐Based Metal‐Free Catalysts

Highly active and durable catalysts play a key role in clean energy technologies. However, the high cost, low reserves, and poor stability of noble‐metal‐based catalysts have hindered the large‐scale development of renewable energy. Owing to their low cost, earth abundance, high activity, and excellent stability, carbon‐based metal‐free catalysts (CMFCs) are promising alternatives to precious‐metal‐based catalysts. Although many synthetic methods based on solution, surface/interface, solid state, and noncovalent chemistries have been developed for producing numerous CMFCs with diverse structures and functionalities, there is still a lack of effective approaches to precisely control the structures of active sites. Therefore, novel chemical approaches are needed for the development of highly active and durable CMFCs that are capable of replacing precious‐metal catalysts for large‐scale applications. Herein, a comprehensive and critical review on chemical approaches to CMFCs is given by summarizing important advancements, current challenges, and future perspectives in this emerging field. Through such a critical review, our understanding of CMFCs and the associated synthetic processes will be significantly increased.     

Nanostructured Metal‐Free Electrochemical Catalysts for Highly Efficient Oxygen Reduction

Replacing precious and nondurable Pt catalysts with cheap and commercially available materials to facilitate sluggish cathodic oxygen reduction reaction (ORR) is a key issue in the development of fuel cell technology. The recently developed cost effective and highly stable metal‐free catalysts reveal comparable catalytic activity and significantly better fuel tolerance than that of current Pt‐based catalysts; therefore, they can serve as feasible Pt alternatives for the next generation of ORR electrocatalysts. Their promising electrocatalytic properties and acceptable costs greatly promote the R&D of fuel cell technology. This review provides an overview of recent advances in state‐of‐the‐art nanostructured metal‐free electrocatalysts including nitrogen‐doped carbons, graphitic‐carbon nitride (g‐C₃N₄)‐based hybrids, and 2D graphene‐based materials. A special emphasis is placed on the molecular design of these electrocatalysts, origin of their electrochemical reactivity, and ORR pathways. Finally, some perspectives are highlighted on the development of more efficient ORR electrocatalysts featuring high stability, low cost, and enhanced performance, which are the key factors to accelerate the commercialization of fuel cell technology.     

Heteroatom‐Doped Carbon Materials for Hydrazine Oxidation

The key in designing efficient direct liquid fuel cells (DLFCs), which can offer some solutions to society's grand challenges associated with sustainability and energy future, currently lies in the development of cost‐effective electrocatalysts. Among the many types of fuel cells, direct hydrazine fuel cells (DHFCs) are of particular interest, especially due to their high theoretical cell voltages and clean emission. However, DHFCs currently use noble‐metal‐based electrocatalysts, and the scarcity and high cost of noble metals are hindering these fuel cells from finding large‐scale practical applications. In order to replace noble‐metal‐based electrocatalysts with sustainable ones and help DHFCs become widely usable, great efforts are being made to develop stable heteroatom (e.g., B, N, O, P and S)‐doped carbon electrocatalysts, the activities of which are comparable to, or better than, those of noble metals. Here, the recent research progress and the advancements made on the development of heteroatom‐doped carbon materials, their general properties, their electrocatalytic activities toward the HzOR, and their dopant‐ and structure‐related electrocatalytic properties for the HzOR are summarized. Perspectives on the different directions that the research endeavors in this field need to take in the future and the challenges associated with DHFCs are included.     

Selective Growth of Metal‐Free Metallic and Semiconducting Single‐Wall Carbon Nanotubes

A major obstacle for the use of single‐wall carbon nanotubes (SWCNTs) in electronic devices is their mixture of different types of electrical conductivity that strongly depends on their helical structure. The existence of metal impurities as a residue of a metallic growth catalyst may also lower the performance of SWCNT‐based devices. Here, it is shown that by using silicon oxide (SiO_x) nanoparticles as a catalyst, metal‐free semiconducting and metallic SWCNTs can be selectively synthesized by the chemical vapor deposition of ethanol. It is found that control over the nanoparticle size and the content of oxygen in the SiO_x catalyst plays a key role in the selective growth of SWCNTs. Furthermore, by using the as‐grown semiconducting and metallic SWCNTs as the channel material and source/drain electrodes, respectively, all‐SWCNT thin‐film transistors are fabricated to demonstrate the remarkable potential of these SWCNTs for electronic devices.     

Carbon‐Based Metal‐Free ORR Electrocatalysts for Fuel Cells: Past,Present, and Future

Replacing precious platinum with earth‐abundant materials for the oxygen reduction reaction (ORR) in fuel cells has been the objective worldwide for several decades. In the last 10 years, the fastest‐growing branch in this area has been carbon‐based metal‐free ORR electrocatalysts. Great progress has been made in promoting the performance and understanding the underlying fundamentals. Here, a comprehensive review of this field is presented by emphasizing the emerging issues including the predictive design and controllable construction of porous structures and doping configurations, mechanistic understanding from the model catalysts, integrated experimental and theoretical studies, and performance evaluation in full cells. Centering on these topics, the most up‐to‐date results are presented, along with remarks and perspectives for the future development of carbon‐based metal‐free ORR electrocatalysts.     

Sulfur and Nitrogen Co‐Doped Graphene for Metal‐Free Catalytic Oxidation Reactions

Sulfur and nitrogen co‐doped reduced graphene oxide (rGO) is synthesized by a facile method and demonstrated remarkably enhanced activities in metal‐free activation of peroxymonosulfate (PMS) for catalytic oxidation of phenol. Based on first‐order kinetic model, S–N co‐doped rGO (SNG) presents an apparent reaction rate constant of 0.043 ± 0.002 min^?1, which is 86.6, 22.8, 19.7, and 4.5‐fold as high as that over graphene oxide (GO), rGO, S‐doped rGO (S‐rGO), and N‐doped rGO (N‐rGO), respectively. A variety of characterization techniques and density functional theory calculations are employed to investigate the synergistic effect of sulfur and nitrogen co‐doping. Co‐doping of rGO at an optimal sulfur loading can effectively break the inertness of carbon systems, activate the sp²‐hybridized carbon lattice and facilitate the electron transfer from covalent graphene sheets for PMS activation. Moreover, both electron paramagnetic resonance (EPR) spectroscopy and classical quenching tests are employed to investigate the generation and evolution of reactive radicals on the SNG sample for phenol catalytic oxidation. This study presents a novel metal‐free catalyst for green remediation of organic pollutants in water.     

Synthesis and Applications of Graphdiyne‐Based Metal‐Free Catalysts

The development of carbon materials offers the hope for obtaining inexpensive and high‐performance alternatives to substitute noble‐metal catalysts for their sustainable application. Graphdiyne, the rising‐star carbon allotrope, is a big family with many members, and first realized the coexistence of sp‐ and sp²‐hybridized carbon atoms in a 2D planar structure. Different from the prevailing carbon materials, its nonuniform distribution in the electronic structure and wide tunability in bandgap show many possibilities and special inspirations to construct new‐concept metal‐free catalysts, and provide many opportunities for achieving a catalytic activity comparable with that of noble‐metal catalysts. Herein, the recent progress in synthetic methodologies, theoretical predictions, and experimental investigations of graphdiyne for metal‐free catalysts is systematically summarized. Some new perspectives of the opportunities and challenges in developing high‐performance graphdiyne‐based metal‐free catalysts are demonstrated.