Photoreduction of CO2 into sustainable and green solar fuels is generally believed to be an appealing solution to simultaneously overcome both environmental problems and energy crisis. The low selectivity of challenging multi-electron CO2 photoreduction reactions makes it one of the holy grails in heterogeneous photocatalysis. This Review highlights the important roles of cocatalysts in selective photocatalytic CO2 reduction into solar fuels using semiconductor catalysts. A special emphasis in this review is placed on the key role, design considerations and modification strategies of cocatalysts for CO2 photoreduction. Various cocatalysts, such as the biomimetic, metal-based, metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area. This Review provides useful information for the design of highly selective cocatalysts for photo(electro)reduction and electroreduction of CO2 and complements the existing reviews on various semiconductor photocatalysts.

Cocatalysts for Selective Photoreduction of CO2 into Solar Fuels.

Transition metal carbides and nitrides (MXenes), a family of two-dimensional (2D) inorganic compounds, are materials composed of a few atomic layers of transition metal carbides, nitrides, or carbonitrides. Ti3C2, the first 2D layered MXene, was isolated in 2011. This material, which is a layered bulk material analogous to graphite, was derived from its 3D phase, Ti3AlC2 MAX. Since then, material scientists have either determined or predicted the stable phases of >200 different MXenes based on combinations of various transition metals such as Ti, Mo, V, Cr, and their alloys with C and N. Extensive experimental and theoretical studies have shown their exciting potential for energy conversion and electrochemical storage. To this end, we comprehensively summarize the current advances in MXene research. We begin by reviewing the structure types and morphologies and their fabrication routes. The review then discusses the mechanical, electrical, optical, and electrochemical properties of MXenes. The focus then turns to their exciting potential in energy storage and conversion. Energy storage applications include electrodes in rechargeable lithium- and sodium-ion batteries, lithium-sulfur batteries, and supercapacitors. In terms of energy conversion, photocatalytic fuel production, such as hydrogen evolution from water splitting, and carbon dioxide reduction are presented. The potential of MXenes for the photocatalytic degradation of organic pollutants in water, such as dye waste, is also addressed, along with their promise as catalysts for ammonium synthesis from nitrogen. Finally, their application potential is summarized.

Applications of 2D MXenes in energy conversion and storage systems

Heterocyclic pyrrole molecules are in situ aligned and polymerized in the -absence of an oxidant between layers of the 2D Ti3C2Tx (MXene), resulting in high volumetric and gravimetric capacitances with capacitance retention of 92% after 25,000 cycles at a 100 mV s(-1) scan rate.

Pseudocapacitive Electrodes Produced By Oxidant-Free Polymerization of Pyrrole Between the Layers of 2D Titanium Carbide (MXene)

Ti3 C2 Tx , a typical representative among the emerging family of 2D layered transition metal carbides and/or nitrides referred to as MXenes, has exhibited multiple advantages including metallic conductivity, a plastic layer structure, small band gaps, and the hydrophilic nature of its functionalized surface. As a result, this 2D material is intensively investigated for application in the energy storage field. The composition, morphology and texture, surface chemistry, and structural configuration of Ti3 C2 Tx directly influence its electrochemical performance, e.g., the use of a well-designed 2D Ti3 C2 Tx as a rechargeable battery anode has significantly enhanced battery performance by providing more chemically active interfaces, shortened ion-diffusion lengths, and improved in-plane carrier/charge-transport kinetics. Some recent progresses of Ti3 C2 Tx MXene are achieved in energy storage. This Review summarizes recent advances in the synthesis and electrochemical energy storage applications of Ti3 C2 Tx MXene including supercapacitors, lithium-ion batteries, sodium-ion batteries, and lithium-sulfur batteries. The current opportunities and future challenges of Ti3 C2 Tx MXene are addressed for energy-storage devices. This Review seeks to provide a rational and in-depth understanding of the relation between the electrochemical performance and the nanostructural/chemical composition of Ti3 C2 Tx , which will promote the further development of 2D MXenes in energy-storage applications.

Recent Advances in Layered Ti 3 C 2 T x MXene for Electrochemical Energy Storage

2D MXenes: Electromagnetic property for microwave absorption and electromagnetic interference shielding

The MXenes combining hydrophilic surface, metallic conductivity and rich surface chemistries represent a new family of 2D materials with widespread applications. However, their poor oxygen resistance causes a great loss of electronic properties and surface reactivity, which significantly inhibits the fabrication, the understanding of the chemical nature and full exploitation of the potential of MXene-based materials. Herein we report a facile carbon nanoplating strategy for efficiently stabilizing the MXenes against structural degradation caused by spontaneous oxidation, which provides a material platform for developing MXene-based materials with attractive structure and properties. Hierarchical MoS2 /Ti3 C2 -MXene@C nanohybrids with excellent structural stability, electrical properties and strong interfacial coupling are fabricated by assembling carbon coated few-layered MoS2 nanoplates on carbon-stabilized Ti3 C2 MXene, exhibiting exceptional performance for Li storage and hydrogen evolution reaction (HER). Remarkably, ultra-long cycle life of 3000 cycles with high capacities but extremely slow capacity loss of 0.0016% per cycle is achieved for Li storage at a very high rate of 20 A g-1 . They are also highly active HER electrocatalyst with very positive onset potential, low overpotential and long-term stability in acidic solution. Superb properties highlight the great promise of MXene-based materials in cornerstone applications of energy storage and conversion.

Stabilizing the MXenes by Carbon Nanoplating for Developing Hierarchical Nanohybrids with Efficient Lithium Storage and Hydrogen Evolution Capability.

The MXene combining high conductivity, hydrophilic surface, and wide chemical variety has been recognized as a rapidly rising star on the horizon of two-dimensional (2D) material science. However, strong tendency to intersheet aggregate via van der Waals force represents a major problem limiting the functionalities, processability, and performance of MXene-based material/devices. We report a capillary-forced assembling strategy for processing MXene to hierarchical 3D architecture with geometry-based high resistance to aggregation. Aggregate-resistant properties of 3D MXene not only double the surface area without loss of the intrinsic properties of MXene but also render the characteristics such as kinetics-favorable framework, high robustness, and excellent processability in both solution and solid state. Synergistically coupling the 3D MXene with electrochemically active phases such as metal oxide/phosphides, noble metals, or sulfur yields the hybrid systems with greatly boosted active surface area, charge-transfer kinetics, and mass diffusion rate. Specifically, the CoP-3D MXene hybrids exhibit high electrocatalytic activity toward oxygen and hydrogen evolution in alkaline electrolyte. As a bifunctional electrocatalyst, they exhibit superior cell voltage and durability to combined RuO2/Pt catalysts for overall water splitting in basic solution, highlighting the great promise of aggregation-resistant 3D MXene in the development of high-performance electrocatalysts.

Aggregation-Resistant 3D MXene-Based Architecture as Efficient Bifunctional Electrocatalyst for Overall Water Splitting.

Engineering Multifunctional Collaborative Catalytic Interface Enabling Efficient Hydrogen Evolution in All pH Range and Seawater

Powerful yet thinner lithium-ion batteries (LIBs) are eagerly desired to meet the practical demands of electric vehicles and portable electronic devices. However, the use of soft carbon materials in current electrode design to improve the electrode conductivity and stability does not afford high volumetric capacity due to their low density and capacity for lithium storage. Herein, we report a strategy leveraging the MXene with superior conductivity and density to soft carbon as matrix and additive material for comprehensively enhancing the power capability, lifespan, and volumetric capacity of conversion-type anode. A kinetics favorable 2D nanohybrid with high conductivity, compact density, accumulated pseudocapacitance, and diffusion-controlled behavior is fabricated by coupling Ti3C2 MXene with high-density molybdenum carbide for fast lithium storage over 300 cycles with high capacities. By replacing the carbonaceous conductive agent with Ti3C2 MXene, the electrodes with better conductivity and dramatic...

MXene-Based Electrode with Enhanced Pseudocapacitance and Volumetric Capacity for Power-Type and Ultra-Long Life Lithium Storage

Seawater electrolysis represents a potential solution to grid-scale production of carbon-neutral hydrogen energy without reliance on freshwater. However, it is challenged by high energy costs and detrimental chlorine chemistry in complex chemical environments. Here we demonstrate chlorine-free hydrogen production by hybrid seawater splitting coupling hydrazine degradation. It yields hydrogen at a rate of 9.2 mol h–1 gcat–1 on NiCo/MXene-based electrodes with a low electricity expense of 2.75 kWh per m3 H2 at 500 mA cm–2 and 48% lower energy equivalent input relative to commercial alkaline water electrolysis. Chlorine electrochemistry is avoided by low cell voltages without anode protection regardless Cl– crossover. This electrolyzer meanwhile enables fast hydrazine degradation to ~3 ppb residual. Self-powered hybrid seawater electrolysis is realized by integrating low-voltage direct hydrazine fuel cells or solar cells. These findings enable further opportunities for efficient conversion of ocean resources to hydrogen fuel while removing harmful pollutants. Seawater electrolysis is promising for grid-scale H2 production without freshwater reliance, but high energy costs and detrimental Cl chemistry reduce its practical potential. Here, authors developed an energy-saving hybrid seawater electrolyzer for chlorine-free H2 production and N2H4 degradation.

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Xianhong Wu

Papers

Stabilizing the MXenes by Carbon Nanoplating for Developing Hierarchical Nanohybrids with Efficient Lithium Storage and Hydrogen Evolution Capability.

Aggregation-Resistant 3D MXene-Based Architecture as Efficient Bifunctional Electrocatalyst for Overall Water Splitting.

Engineering Multifunctional Collaborative Catalytic Interface Enabling Efficient Hydrogen Evolution in All pH Range and Seawater

MXene-Based Electrode with Enhanced Pseudocapacitance and Volumetric Capacity for Power-Type and Ultra-Long Life Lithium Storage

Energy-saving hydrogen production by chlorine-free hybrid seawater splitting coupling hydrazine degradation.