Steering sp-Carbon Content in Graphdiynes for Enhanced Two-Electron Oxygen Reduction to Hydrogen Peroxide.

Compared to sp2-hybridized graphene, graphdiynes (GDYs) composed of sp and sp2 carbon are highly promising as efficient catalysts for electrocatalytic oxygen reduction into oxygen peroxide because of the high catalytic reactivity of the electron-rich sp-carbon atoms. The desired catalytic capacity of GDY, such as catalytic selectivity and efficiency, can theoretically be achieved by strategically steering the sp-carbon contents or the topological arrangement of the acetylenic linkages and aromatic bonds. Herein, we successfully tuned the electrocatalytic activity of GDYs by regulating the sp-to-sp2 carbon ratios with different organic monomer precursors. As the active sp-carbon atoms possess electron-sufficient π orbitals, they can donate electrons to the lowest unoccupied molecular orbital (LUMO) orbitals of O2 molecules and initiate subsequent O2 reduction, GDY with the high sp-carbon content of 50 at % exhibits excellent capability of catalyzing O2 reduction into H2O2. It demonstrates exceptional H2O2 selectivity of over 95.0 % and impressive performance in practical H2O2 production, Faraday efficiency (FE) exceeding 99.0 %, and a yield of 83.3 nmol s-1 cm-2. Our work holds significant importance in effectively steering the inherent properties of GDYs by purposefully adjusting the sp-to-sp2 carbon ratio and highlights their immense potential for research and applications in catalysis and other fields.

sp-Carbon-Conjugated Organic Polymer as Multifunctional Interfacial Layers for Ultra-Long Dendrite-Free Lithium Metal Batteries.

Fatal issues in lithium metal anodes (LMA), such as detrimental lithium dendrites growth and fragile solid-electrolyte interphase (SEI) during the Li plating/stripping process, often hinder the practical application of Li metal batteries (LMBs). Herein, cobalt-coordinated sp-carbon-conjugated organic polymer (Co-spc-COP) is constructed as the protective layer for regulating the interface stability of LMA. The unique synergistic beneficial effect of organic functional groups (C≡C linkage, C=N units and aromatic rings) and Co sites not only regulate the Li+ coordination environment and rearrange Li+ concentration to facilitate its transport by optimizing the electronic density, enhancing the compatibility with electrolyte interface and supplying "external magnetic driving strategy", but also strengthens the interfacial stiffness with high Young's modulus to better withstand the mechanical stress. These beneficial effects and relative underlying working mode and mechanism of uniform Li plating and rapid Li+ migration on the Co-spc-COP are also revealed by various in situ/ex situ experimental technologies and theory calculation. The Co-spc-COP-based cell delivers an extraordinary lifespan of 6600 h and ultrahigh capacity retention of 78.3 % (111.9 mAh g-1) after 1000 cycles at 1 C. This demonstrated synergistic strategy in Co-coordinated organic polymer may gain new insights to regulate the uniform and non-dendritic deposition/dissolution behaviors for highly stable LMBs.

sp-Carbon Incorporated Conductive Metal-Organic Framework as Photocathode for Photoelectrochemical Hydrogen Generation.

Metal-organic frameworks (MOFs) have attracted increasing interest for broad applications in catalysis and gas separation due to their high porosity. However, the insulating feature and the limited active sites hindered MOFs as photocathode active materials for application in photoelectrocatalytic hydrogen generation. Herein, we develop a layered conductive two-dimensional conjugated MOF (2D c-MOF) comprising sp-carbon active sites based on arylene-ethynylene macrocycle ligand via CuO4 linking, named as Cu3 HHAE2 . This sp-carbon 2D c-MOF displays apparent semiconducting behavior and broad light absorption till the near-infrared band (1600 nm). Due to the abundant acetylene units, the Cu3 HHAE2 could act as the first case of MOF photocathode for photoelectrochemical (PEC) hydrogen generation and presents a record hydrogen-evolution photocurrent density of ≈260 µA cm-2 at 0 V vs. reversible hydrogen electrode among the structurally-defined cocatalyst-free organic photocathodes.

Titanium-Based Metasurfaces for Optoelectronics.

We report on the fabrication method that enables the development of transparent conductive metasurfaces capable of the resonant absorption of light in specific frequency bands. The approach is based on embedding linear sp-carbon chains and metallic nanoparticles in a porous matrix of titanium dioxide (TiO2). We develop a blading technique for the formation of a periodical grating of TiO2 microtubes at the macroscale. The method allowed us to maintain the periodicity of an array of microtubes with an accuracy of ±5%. Tuning the diameter of the tubes and the concentration of metallic nanoparticles, we achieved the regime of strong resonant absorption of the fabricated complex metasurface in the visible range. Computer simulations helped revealthe regime of TE/TM-polarized laser pumping that allowed for the most efficient transformation of light energy into electric current flow. In the studied structures, the sp-carbon clusters embedded inside transparent titanium dioxide tubes play the role of atomic wires. The interplay between efficient conductivity through carbon wires and the plasmon-enhanced absorption of light allows the design of photodiode structures based on periodical metasurfaces and characterized by highly selective optical sensitivity.

Stable and Solution-Processable Cumulenic sp-Carbon Wires: A New Paradigm for Organic Electronics.

Solution-processed, large-area, and flexible electronics largely relies on the excellent electronic properties of sp2 -hybridized carbon molecules, either in the form of π-conjugated small molecules and polymers or graphene and carbon nanotubes. Carbon with sp-hybridization, the foundation of the elusive allotrope carbyne, offers vast opportunities for functionalized molecules in the form of linear carbon atomic wires (CAWs), with intriguing and even superior predicted electronic properties. While CAWs represent a vibrant field of research, to date, they have only been applied sparingly to molecular devices. The recent observation of the field-effect in microcrystalline cumulenes suggests their potential applications in solution-processed thin-film transistors but concerns surrounding the stability and electronic performance have precluded developments in this direction. In the present study, ideal field-effect characteristics are demonstrated for solution-processed thin films of tetraphenyl[3]cumulene, the shortest semiconducting CAW. Films are deposited through a scalable, large-area, meniscus-coating technique, providing transistors with hole mobilities in excess of 0.1 cm2  V-1  s-1 , as well as promising operational stability under dark conditions. These results offer a solid foundation for the exploitation of a vast class of molecular semiconductors for organic electronics based on sp-hybridized carbon systems and create a previously unexplored paradigm.

On-Surface Synthesis of sp-Carbon Nanostructures.

The on-surface synthesis of carbon nanostructures has attracted tremendous attention owing to their unique properties and numerous applications in various fields. With the extensive development of scanning tunneling microscope (STM) and noncontact atomic force microscope (nc-AFM), the on-surface fabricated nanostructures so far can be characterized on atomic and even single-bond level. Therefore, various novel low-dimensional carbon nanostructures, challenging to traditional solution chemistry, have been widely studied on surfaces, such as polycyclic aromatic hydrocarbons, graphene nanoribbons, nanoporous graphene, and graphyne/graphdiyne-like nanostructures. In particular, nanostructures containing sp-hybridized carbons are of great advantage for their structural linearity and small steric demands as well as intriguing electronic and mechanical properties. Herein, the recent developments of low-dimensional sp-carbon nanostructures fabricated on surfaces will be summarized and discussed.