Direct conversion of CO2 to CH4 on Pd/graphdiyne single-crystalline.

A major impediment to the development of the efficient use of artificial photosynthesis is the lack of highly selective and efficient photocatalysts toward the conversion of CO2 by sunlight energy at room temperature and ambient pressure. After many years of hard work, we finally completed the synthesis of graphdiyne-based palladium quantum dot catalysts containing high-density metal atom steps for selective artificial photosynthesis. The well-designed interface structure of the catalyst is composed of electron-donor and acceptor groups, resulting in the obvious incomplete charge-transfer phenomenon between graphdiyne and plasmonic metal nanostructures on the interface. These intrinsic characteristics are the origin of the high performance of the catalyst. Studies on its mechanism reveal that the synergism between 'hot electron' from local surface plasmon resonance and rapid photogenerated carrier separation at the ohmic contact interface accelerates the multi-electron reaction kinetics. The catalyst can selectively synthesize CH4 directly from CO2 and H2O with selectivity of near 100% at room temperature and pressure, and exhibits transformative performance, with an average CH4 yield of 26.2 µmol g-1 h-1 and remarkable long-term stability.

Confined Growth of Highly Ordered Metal Atomic Arrays for Seawater Oxidation.

Metal atom catalysts have been among the most important research objects due to their specific physical and chemical properties. However, precise control of the anchoring of metal atoms is still challenging to achieve. Cobalt and iridium atomic arrays formed sequentially ordered stable arrays in graphdiyne (GDY) triangular cavities depending on their intrinsic chemical properties and interactions. The success of this method was attributed to multifunctional integration of GDY, enabling selective growth from one to several atoms and various atomic densities. The bimetallic atom arrays show several advantages resulting from reducibility of acetylene bonds, space limiting effect, incomplete charge transfer between GDY and metal atoms, and sp-C hybridized triple bond skeleton. This well-designed system exhibits unprecedented oxygen evolution reaction (OER) performance with a mass activity of 2.6 A mgcat.-1 at a low overpotential of 300 mV, which is 216.6 times higher than the state-of-the-art IrO2 catalyst, and long-term stability.

A Multi-Interface Structure of Graphdiyne/Cobalt Oxides for Chlorine Production.

A challenge facing the chlor-alkali process is the lack of electrocatalyst with high activity and selectivity for the efficient industrial production of chlorine. Herein the authors report a new electrocatalyst that can generate multi-interface structure by in situ growth of graphdiyne on the surface of cobalt oxides (GDY/Co3O4), which shows great potential in highly selective and efficient chlorine production. This result is due to the strong electron transfer and high density charge transport between GDY and Co3O4 and the interconversion of the mixed valence states of the Co atoms itself. These intrinsic characteristics efficiently enhance the conductivity of the catalyst, facilitate the reaction kinetics, and improve the overall catalytic selectivity and activity. Besides, the protective effect of the formed GDY layer is remarkable endowing the catalyst with excellent stability. The catalyst can selectively produce chlorine in low-concentration of NaCl aqueous solution at room temperature and pressure with the highest Faraday efficiency of 80.67% and an active chlorine yield rate of 184.40 mg h-1 cm-2, as well as superior long-term stability.

Self-Organized Gradually Single-Atom-Layer of Metal Osmium for an Unprecedented Hydrogen Production from Seawater.

Atomic thick two-dimensional (2D) materials with exciting physical, chemical, and electronic properties are gaining increasing attention in next-generation science and technology, showing great promise in catalysis and energy science. However, the precise design and synthesis of efficient catalytic systems based on such materials still face many difficulties, especially in how to control the preparation of structurally determined, highly active, atomic-scale distribution of material systems. Here, we report that a highly active zerovalent osmium single-atom-layer with a thickness of single atom size has been successfully and controllably self-organized on the surface of 2D graphdiyne (GDY) material. Detailed characterizations showed that the incomplete charge transfer effect between the Os atoms and GDY not only stabilized the catalytic system but also improved the intrinsic activity, making the Gibbs free energy reach the best and resulting in remarkable performance with a small overpotential of 49 mV at 500 mA cm-2, large specific j0 of 18.6 mA cm-2, and turnover frequency of 3.89 H2 s-1 at 50 mV. In addition, the formation of sp-C-Os bonds guarantees the high long-term stability of 800 h at a large current density of 500 mA cm-2 in alkaline simulated seawater.

Theoretical Prediction Leads to Synthesize GDY Supported InOx Quantum Dots for CO2 Reduction.

The preparation of formic acid by direct reduction of carbon dioxide is an important basis for the future chemical industry and is of great significance. Due to the serious shortage of highly active and selective electrocatalysts leading to the development of direct reduction of carbon dioxide is limited. Herein the target catalysts with high CO2RR activity and selectivity were identified by integrating DFT calculations and high-throughput screening and by using graphdiyne (GDY) supported metal oxides quantum dots (QDs) as the ideal model. It is theoretically predicted that GDY supported indium oxide QDs (i.e., InOx/GDY) is a new heterostructure electrocatalyst candidate with optimal CO2RR performance. The interfacial electronic strong interactions effectively regulate the surface charge distribution of QDs and affect the adsorption/desorption behavior of HCOO* intermediate during CO2RR to achieve highly efficient CO2 conversion. Based on the predicted composition and structure, we synthesized the advanced catalytic system, and demonstrates superior CO2-to-HCOOH conversion performance. The study presents an effective strategy for rational design of highly efficient heterostructure electrocatalysts to promote green chemical production.

Controlled Growth of Metal Atom Arrays on Graphdiyne for Seawater Oxidation.

Advanced atomic-level heterointerface engineering provides a promising method for the preparation of next-generation catalysts. Traditional carbon-based heterointerface catalytic performance rely heavily on the undetermined defects in complex and demanding preparation processes, rendering it impossible to control the catalytic performance. Here, we present a general method for the controlled growth of metal atom arrays on graphdiyne (GDY/IrCuOx), and we are surprised to find strong heterointerface strains during the growth. We successfully controlled the thickness of GDY to regulate the heterointerface metal atoms and achieved compressive strain at the interface. Experimental and density functional theory calculation results show that the unique incomplete charge transfer between GDY and metal atoms leads to the formation of strong interactions and significant heterointerface compressive strain between GDY and IrCuOx, which results in high oxidation performances with 1000 mA cm-2 at a low overpotential of 283 mV and long-term stability at large current densities in alkaline simulated seawater. We anticipate that this finding will contribute to construction of high-performance heterogeneous interface structures, leading to the development of new generation of GDY-based heterojunction catalysts in the field of catalysis for future promising performance.

Controllable Assembly of Highly Oxidized Cobalt on Graphdiyne Surface for Efficient Conversion of Nitrogen into Nitric Acid.

The manufacture of nitric acid (HNO3 ) consumes large amounts of energy and causes serious environmental pollution. Electrochemical synthesis is regarded as a key way to eliminate carbon emissions from the chemicals industry. The selective electrosynthesis of HNO3 from nitrogen was achieved by controllable assembly of cobalt metal on graphdiyne surface using a powerful tool of electrochemistry at ambient conditions. As an advanced material, graphdiyne (GDY) has a large conjugated structure on its surface and is rich in sp-C triple bond skeleton, which can achieve strong interaction with metal atoms, resulting in incomplete charge transfer between graphdiyne and cobalt atoms. The experimental and theoretical calculation results show that the highly oxidized cobalt on graphdiyne (HOCo/GDY) can selectively and efficiently activate and convert the nitrogen into the key intermediate *NO, which promotes the efficient overall conversion performance of nitrogen to nitric acid. Thus, the highest nitric acid yield (192.0 µg h-1 mg-1 ) and Faradaic efficiency (21.5 %) were achieved at low potentials.

Alkyne-to-alkene conversion in graphdiyne driving instant reversible deformation of whole carbon film.

The emerging field of soft robotics demands the core actuators and related responsive functional materials with rapid responsiveness and controllable accurate deformation. Here, we developed an alkyne-to-alkene chemical bond conversion way as the driving force to control ultrasensitive and instant reversible deformation of 2D carbon graphdiyne (GDY) film with an asymmetric interface design. The alkyne-to-alkene chemical bond conversion was triggered by acetone through the fast binding and release process. The as-fabricated GDY-based deformation modulator was exhibited to rapidly change shape (within 0.15 seconds) while dipped in an acetone vapor atmosphere and recover to its original form when exposed to air (recovery time < 0.01 seconds), with outstanding properties like large curvature, quick recovery time, excellent stability, and repeatability. It could mimic the movement of mosquito larvae, displaying great promise as micro bionic soft robots. Our results suggest alkyne-to-alkene bond conversion as a unique driving force for developing smart materials for areas like intelligent robotics and bionics.

Highly Selective Electrocatalytic Olefin Hydrogenation in Aqueous Solution.

Selective hydrogenation of olefins with water as the hydrogen source at ambient conditions is still a big challenge in the field of catalysis. Herein, the electrocatalytic hydrogenation of purely aliphatic and functionalized olefins was achieved by using graphdiyne based copper oxide quantum dots (Cux O/GDY) as cathodic electrodes and water as the hydrogen source, with high activity and selectivity in aqueous solution at high current density under ambient temperature and pressure. In particular, the sp-/sp2 -hybridized graphdiyne catalyst allows the selective hydrogenation of cis-trans isomeric olefins. The chemical and electronic structure of the GDY results in the incomplete charge transfer between GDY and Cu atoms to optimize the adsorption/desorption of the reaction intermediates and results in high reaction selectivity and activity for hydrogenation reactions.

Graphdiyne-Based Multiscale Catalysts for Ammonia Synthesis.

Graphdiyne, a sp/sp2 -cohybridized two-dimensional all- carbon material, has many unique and fascinating properties of alkyne-rich structures, large π conjugated system, uniform pores, specific unevenly-distributed surface charge, and incomplete charge transfer properties provide promising potential in practical applications including catalysis, energy conversion and storage, intelligent devices, life science, photoelectric, etc. These superior advantages have made graphdiyne one of the hottest research frontiers of chemistry and materials science and produced a series of original and innovative research results in the fundamental and applied research of carbon materials. In recent years, considerable advances have been made toward the development of graphdiyne-based multiscale catalysts for nitrogen fixation and ammonia synthesis at room temperatures and ambient pressures. This review aims to provide a comprehensive update in regard to the synthesis of graphdiyne-based multiscale catalysts and their applications in the synthesis of ammonia. The unique features of graphdiyne are highlighted throughout the review. Finally, it concludes with the discussion of challenges and future perspectives relating to graphdiyne.

Ir0/graphdiyne atomic interface for selective epoxidation.

The development of catalysts that can selectively and efficiently promote the alkene epoxidation at ambient temperatures and pressures is an important promising path to renewable synthesis of various chemical products. Here we report a new type of zerovalent atom catalysts comprised of zerovalent Ir atoms highly dispersed and anchored on graphdiyne (Ir0/GDY) wherein the Ir0 is stabilized by the incomplete charge transfer effect and the confined effect of GDY natural cavity. The Ir0/GDY can selectively and efficiently produce styrene oxides (SO) by electro-oxidizing styrene (ST) in aqueous solutions at ambient temperatures and pressures with high conversion efficiency of ∼100%, high SO selectivity of 85.5%, and high Faradaic efficiency (FE) of 55%. Experimental and density functional theory (DFT) calculation results show that the intrinsic activity and stability due to the incomplete charge transfer between Ir0 and GDY effectively promoted the electron exchange between the catalyst and reactant molecule, and realized the selective epoxidation of ST to SO. Studies of the reaction mechanism demonstrate that Ir0/GDY proceeds a distinctive pathway for highly selective and active alkene-to-epoxide conversion from the traditional processes. This work presents a new example of constructing zerovalent metal atoms within the GDY matrix toward selective electrocatalytic epoxidation.

Two-Dimensional Carbon Graphdiyne: Advances in Fundamental and Application Research.

Graphdiyne (GDY), a rising star of carbon allotropes, features a two-dimensional all-carbon network with the cohybridization of sp and sp2 carbon atoms and represents a trend and research direction in the development of carbon materials. The sp/sp2-hybridized structure of GDY endows it with numerous advantages and advancements in controlled growth, assembly, and performance tuning, and many studies have shown that GDY has been a key material for innovation and development in the fields of catalysis, energy, photoelectric conversion, mode conversion and transformation of electronic devices, detectors, life sciences, etc. In the past ten years, the fundamental scientific issues related to GDY have been understood, showing differences from traditional carbon materials in controlled growth, chemical and physical properties and mechanisms, and attracting extensive attention from many scientists. GDY has gradually developed into one of the frontiers of chemistry and materials science, and has entered the rapid development period, producing large numbers of fundamental and applied research achievements in the fundamental and applied research of carbon materials. For the exploration of frontier scientific concepts and phenomena in carbon science research, there is great potential to promote progress in the fields of energy, catalysis, intelligent information, optoelectronics, and life sciences. In this review, the growth, self-assembly method, aggregation structure, chemical modification, and doping of GDY are shown, and the theoretical calculation and simulation and fundamental properties of GDY are also fully introduced. In particular, the applications of GDY and its formed aggregates in catalysis, energy storage, photoelectronic, biomedicine, environmental science, life science, detectors, and material separation are introduced.

Scalable synthesis of soluble crystalline ionic-graphdiyne by controlled ion expansion.

Graphdiyne (GDY) is a promising material possessing extensive electronic tunability, high π conjugacy, and ordered porosity at a molecular level for the sp/sp2-hybridized periodic structures. Despite these advantages, the preparation of soluble and crystalline graphdiyne is limited by the relatively compact stacking interactions, mostly existing in thick-layer and insoluble solids. Herein, we proposed a strategy of "framework charge-induced intercalation (FCII)" for the synthesis of a soluble (4.3 mg ml-1) and yet interlayer-expanded (∼0.6 Å) crystalline ionic graphdiyne, named as N+-GDY, through regulating the interlayer interactions. The skeleton of such a sample is positively charged, and then the negative ions migrate to the interlayer to expand the space, endowing the N+-GDY with solution processability. The crystal structure of N+-GDY is proved through analysis of HR-TEM images under different axes of observation and theoretical simulations. The resulting N+-GDY possesses high dispersity in organic solvents to produce a pure-solution phase which is conducive to the formation of oriented N+-GDY films, accompanied by exfoliation-nanosheet restacking. The film exhibits a conductivity of 0.014 S m-1, enabling its applications in electronic devices.

In situ growth of a GDY-MnOx heterointerface for selective and efficient ammonia production.

The development of new catalysts with high selectivity and efficiency for the electrocatalytic nitrate reduction reaction (NtRR) to produce ammonia (NH3) at room temperature and ambient pressure is still a challenge. Herein, we report a simple in situ growth method for the controlled synthesis of a GDY-MnOx heterointerface by selectively anchoring and growing MnOx on GDY surfaces. Experimental results show that the incomplete charge-transfer between GDY and Mn atoms at the interface structures largely increases the number of active sites, improves the electrical conductivity, and therefore results in excellent electrocatalytic performance for NH3 synthesis with a maximum FE of 95.4%, an NH3 yield rate of 463.4 µmol h-1 cm-2 and high long-term stability in 0.1 M KOH + 0.1 M NO3- aqueous electrolytes at room temperature and ambient pressure.

Multi-heterointerfaces for selective and efficient urea production.

A major impediment to industrial urea synthesis is the lack of catalysts with high selectivity and activity, which inhibits the efficient industrial production of urea. Here, we report a new catalyst system suitable for the highly selective synthesis of industrial urea by in situ growth of graphdiyne on the surface of cobalt-nickel mixed oxides. Such a catalyst is a multi-heterojunction interfacial structure resulting in the obvious incomplete charge-transfer phenomenon between a graphdiyne and metal oxide interface and multiple intermolecular interactions. These intrinsic characteristics are the origin of the high performance of the catalyst. Studies on the mechanism reveal that the catalyst could effectively optimize the adsorption/desorption capacities of the intermediate and promote direct C-N coupling by significantly suppressing by-product reactions toward the formation of H2, CO, N2 and NH3. The catalyst can selectively synthesize urea directly from nitrite and carbon dioxide in water at room temperature and pressure, and exhibits a record-high Faradaic efficiency of 64.3%, nitrogen selectivity (Nurea-selectivity) of 86.0%, carbon selectivity (Curea-selectivity) of ∼100%, as well as urea yield rates of 913.2 µg h-1 mgcat -1 and remarkable long-term stability.

Step by Step Induced Growth of Zinc-Metal Interface on Graphdiyne for Aqueous Zinc-Ion Batteries.

Rechargeable aqueous zinc ion batteries (AZIBs) promise high energy density, low redox potential, low cost and safety; however, their cycle performances are seriously insufficient to restrict the progress in this field. We propose a new concept of atomic electrode formed on the graphdiyne (GDY). This new idea electrode was synthesized by selectively, uniformly, and stably anchoring Zn atoms on GDY at the beginning of plating. The Zn atoms are induced to grow into larger size Zn clusters, which continue to grow into nanoflat. Finally, a new heterojunction interface is formed on GDY without any Zn dendrites and side reactions, even at high current densities. Such stepwise induction of growth greatly suppresses the formation of Zn dendrites, resulting in high electroplating/stripping reversibility and lifespan of AZIBs.

Synthesis of Crystalline Phosphine-Graphdiyne with Self-Adaptive p-π Conjugation.

"Dynamic" behavior materials with high surface activity and the ability of chemical bond conversion are the frontier materials in the field of renewable energy. The outstanding feature of these materials is that they have adaptive electronic properties that external stimuli can adjust. An original discovery in a new crystalline two-dimensional phosphine-graphdiyne (P-GDY) material is described here. Although the p-π conjugation of most trivalent phosphorus π-systems is insignificant because of the pyramidal configuration, the lone pair electrons of phosphorus atoms participate strongly in the delocalization under the influence of the interlayer van der Waals forces in P-GDY. Due to the dynamically reversible nature of noncovalent interactions (p-π conjugation), P-GDY exhibits a specific adaptive behavior and realizes the responsive reversible transport of a lithium ion by regulating p-π interactions. Our findings would provide the potential to develop a new family of responsive materials with tunable structures.

High energy density primary cathode with a mixed electron/ion interface.

An effective and original strategy described as two-dimensional encapsulation is designed to prepare a high-performance fluorinated carbon cathode composed of a fluorinated carbon/graphdiyne heterostructure (CFx/GDY). The GDY layers of CFx/GDY strengthened the three-dimensional contacts between the CFx particles and additive, achieving outstanding charge transport kinetics and accelerating the lithium-ion diffusion dynamic behavior. The obtained electrodes exhibited a significantly enhanced voltage platform of ∼2.5 V, improved battery rate performance (5C, 621.6 mA h g-1) and energy density with 2039.3 W h kg-1. The excellent storage kinetics can be ascribed to the electronic structure modulation of fluorinated carbon from GDY, and the hierarchical porosity of GDY to create an effective, stable electron transfer and robust ion transportation. Our results demonstrated that two-dimensional GDY encapsulation has enormous potential in improving the performance of lithium primary batteries.

Rhodium nanocrystals on porous graphdiyne for electrocatalytic hydrogen evolution from saline water.

The realization of the efficient hydrogen conversion with large current densities at low overpotentials represents the development trend of this field. Here we report the atomic active sites tailoring through a facile synthetic method to yield well-defined Rhodium nanocrystals in aqueous solution using formic acid as the reducing agent and graphdiyne as the stabilizing support. High-resolution high-angle annular dark-field scanning-transmission electron microscopy images show the high-density atomic steps on the faces of hexahedral Rh nanocrystals. Experimental results reveal the formation of stable sp-C~Rh bonds can stabilize Rh nanocrystals and further improve charge transfer ability in the system. Experimental and density functional theory calculation results solidly demonstrate the exposed high active stepped surfaces and various metal atomic sites affect the electronic structure of the catalyst to reduce the overpotential resulting in the large-current hydrogen production from saline water. This exciting result demonstrates unmatched electrocatalytic performance and highly stable saline water electrolysis.

Controlled growth of a high selectivity interface for seawater electrolysis.

Overall seawater electrolysis is an important direction for the development of hydrogen energy conversion. The key issues include how to achieve high selectivity, activity, and stability in seawater electrolysis reactions. In this report, the heterostructures of graphdiyne-RhOx-graphdiyne (GDY/RhOx/GDY) were constructed by in situ-controlled growth of GDY on RhOx nanocrystals. A double layer interface of sp-hybridized carbon-oxide-Rhodium (sp-C∼O-Rh) was formed in this system. The microstructures at the interface are composed of active sites of sp-C∼O-Rh. The obvious electron-withdrawing surface enhances the catalytic activity with orders of magnitude, while the GDY outer of the metal oxides guarantees the stability. The electron-donating and withdrawing sp-C∼O-Rh structures enhance the catalytic activity, achieving high-performance overall seawater electrolysis with very small cell voltages of 1.42 and 1.52 V at large current densities of 10 and 500 mA cm-2 at room temperatures and ambient pressures, respectively. The compositional and structural superiority of the GDY-derived sp-C-metal-oxide active center offers great opportunities to engineer tunable redox properties and catalytic performance for seawater electrolysis and beyond. This is a typical successful example of the rational design of catalytic systems.