Energy is an indispensable component in the development of modern society. Nanostructured transition metal phosphides (TMPs) have recently emerged as versatile and efficient catalysts in the fields of clean production of fossil fuels, renewable energies, and energy storage technologies. In this review, popular strategies to fabricate TMPs are initially summarized. Then, we present the diverse applications of TMPs as active catalysts in thermocatalysis, electrocatalysis, photocatalysis, and energy storage techniques, with special emphasis on the dependence of reaction activities on the features of TMPs. Throughout the various applications of TMPs, it can be inferred that TMPs themselves play key roles in some cases. While in other cases, it is the synergistic effect of surface oxidation and intrinsic TMPs that is responsible for the high reaction performances. At last, the future perspectives of TMPs are pointed out.

Recent advances in nanostructured transition metal phosphides: synthesis and energy-related applications

Plasmonic nanomaterials coupled with catalytically active surfaces can provide unique opportunities for various catalysis applications, where surface plasmons produced upon proper light excitation can be adopted to drive and/or facilitate various chemical reactions. A brief introduction to the localized surface plasmon resonance and recent design and fabrication of highly efficient plasmonic nanostructures, including plasmonic metal nanostructures and metal/semiconductor heterostructures is given. Taking advantage of these plasmonic nanostructures, the following highlights summarize recent advances in plasmon-driven photochemical reactions (coupling reactions, O2 dissociation and oxidation reactions, H2 dissociation and hydrogenation reactions, N2 fixation and NH3 decomposition, and CO2 reduction) and plasmon-enhanced electrocatalytic reactions (hydrogen evolution reaction, oxygen reduction reaction, oxygen evolution reaction, alcohol oxidation reaction, and CO2 reduction). Theoretical and experimental approaches for understanding the underlying mechanism of surface plasmon are discussed. A proper discussion and perspective of the remaining challenges and future opportunities for plasmonic nanomaterials and plasmon-related chemistry in the field of energy conversion and storage is given in conclusion.

Recent Advances in Plasmonic Nanostructures for Enhanced Photocatalysis and Electrocatalysis.

Precise atomic-level control of composition and geometric structure at the interface between two catalyst components can effectively tune the catalytic properties. Herein, we found a “chimney effect” formed on the interface between the metal oxide and Nickel metal for the hydrogen evolution reaction, using density functional theory calculations and experimental methods. This special chemical environment around the interface leads the neighboring sites to be immune to the H2O* and OH* adsorption and to only selectively adsorb H* properly. Meanwhile, it is also beneficial for the smooth adsorption of the reactant (H*) on the interface and the easy desorption of the product (H2) from the catalyst surface (ΔGH* close to zero). This phenomenon appears similar to a chimney of hydrogen evolution around the metal oxide/metal interface. Such “chimney effect” is a result of the interfacial charge transfer between the metal and metal oxide, and should be the nature of the interface-induced synergistic effect in metal oxide/metal composite catalysts for HER. Experiments further confirm that the catalytic activity of metal oxide/metal composites for HER can be enhanced by increasing the amount of the chimney - the interfacial metal atoms.

Chimney effect of the interface in metal oxide/metal composite catalysts on the hydrogen evolution reaction

Promoting Electrocatalytic Hydrogen Evolution Reaction and Oxygen Evolution Reaction by Fields: Effects of Electric Field, Magnetic Field, Strain, and Light

Metal phosphides (MPs) with unique and desirable physicochemical properties provide promising potential in practical applications, such as the catalysis, gas/humidity sensor, environmental remediation, and energy storage fields, especially for transition metal phosphides (TMPs) and MPs consisting of group IIIA and IVA metal elements. Most studies, however, on the synthesis of MP nanomaterials still face intractable challenges, encompassing the need for a more thorough understanding of the growth mechanism, strategies for large-scale synthesis of targeted high-quality MPs, and practical achievement of functional applications. This review aims at providing a comprehensive update on the controllable synthetic strategies for MPs from various metal sources. Additionally, different passivation strategies for engineering the structural and electronic properties of MP nanostructures are scrutinized. Then, we showcase the implementable applications of MP-based materials in emerging sustainable catalytic fields including electrocatalysis, photocatalysis, mild thermocatalysis, and related hybrid systems. Finally, we offer a rational perspective on future opportunities and remaining challenges for the development of MPs in the materials science and sustainable catalysis fields.

Nanostructured metal phosphides: from controllable synthesis to sustainable catalysis.

We reported a selective semihydrogenation (deuteration) of numerous terminal and internal alkynes using H2 O (D2 O) as the H (D) source over a Pd-P alloy cathode at a lower potential. P-doping caused the enhanced specific adsorption of alkynes and the promoted intrinsic activity for producing adsorbed atomic hydrogen (H*ads ) from water electrolysis. The semihydrogenation of alkynes could be accomplished at a lower potential with up to 99 % selectivity and 78 % Faraday efficiency of alkene products, outperforming pure Pd and commercial Pd/C. This electrochemical semihydrogenation of alkynes might proceed via a H*ads addition pathway rather than a proton-coupled electron transfer process. The decreased amount of H*ads at a lower potential and the more preferential adsorption of the Pd-P to C≡C π bond than C=C moiety resulted in the excellent alkene selectivity. This method was capable of producing mono-, di-, and tri-deuterated alkenes with up to 99 % deuterium incorporation.

Selective Transfer Semihydrogenation of Alkynes with H2O (D2O) as the H (D) Source over a Pd‐P Cathode

Electrocatalytic alkyne semi-hydrogenation to alkenes with water as the hydrogen source using a low-cost noble-metal-free catalyst is highly desirable but challenging because of their over-hydrogenation to undesired alkanes. Here, we propose that an ideal catalyst should have the appropriate binding energy with active atomic hydrogen (H*) from water electrolysis and a weaker adsorption with an alkene, thus promoting alkyne semi-hydrogenation and avoiding over-hydrogenation. So, surface sulfur-doped and -adsorbed low-coordinated copper nanowire sponges are designedly synthesized via in situ electroreduction of copper sulfide and enable electrocatalytic alkyne semi-hydrogenation with over 99% selectivity using water as the hydrogen source, outperforming a copper counterpart without surface sulfur. Sulfur anion-hydrated cation (S2−-K+(H2O)n) networks between the surface adsorbed S2− and K+ in the KOH electrolyte boost the production of active H* from water electrolysis. And the trace doping of sulfur weakens the alkene adsorption, avoiding over-hydrogenation. Our catalyst also shows wide substrate scopes, up to 99% alkenes selectivity, good reducible groups compatibility, and easily synthesized deuterated alkenes, highlighting the promising potential of this method. Highly selective electrocatalytic semi-hydrogenation of alkynes over a noble-metal-free catalyst is highly desirable. Here, authors synthesize sulfur-containing copper nanowire sponges for selective electrocatalytic alkyne semi-hydrogenation using water as the hydrogen source.

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Converting copper sulfide to copper with surface sulfur for electrocatalytic alkyne semi-hydrogenation with water.

Efficient electrocatalytic alkyne semihydrogenation with potential/time-independent selectivity and Faradaic efficiency (FE) is vital for industrial alkene productions. Here, sulfur-tuned effects and field-induced reagent concentration are proposed to promote electrocatalytic alkyne semihydrogenation. Density functional theory calculations reveal that bulk sulfur anions intrinsically weaken alkene adsorption, and surface thiolates lower the activation energy of water and the Gibbs free energy for H* formation. The finite element method shows high-curvature structured catalyst concentrates K+ by enhancing electric field at the tips, accelerating more H* formation from water electrolysis via sulfur anion–hydrated cation networks, and promoting alkyne transformations. So, self-supported Pd nanotips with sulfur modifiers are developed for electrochemical alkyne semihydrogenation with up to 97% conversion yield, 96% selectivity, 75% FE, and a reaction rate of 465.6 mmol m−2 hour−1. Wide potential window and time irrelevance for high alkene selectivity, good universality, and easy access to deuterated alkenes highlight the promising potential.

https://www.science.org/doi/pdf/10.1126/sciadv.abm9477?download=true

Field-induced reagent concentration and sulfur adsorption enable efficient electrocatalytic semihydrogenation of alkynes

Electrocatalytic hydrogen evolution from water splitting holds great promise for renewable energy conversion and usage, but its application is limited by high energy consumption. The development of a facile strategy to efficiently improve the efficiency of energy conversion and the sluggish reaction kinetics using low-cost and stable electrocatalysts is crucial but still highly challenging. Recently, light irradiation is demonstrated to be an efficient external driving force for improving the hydrogen evolution reaction (HER) activities of electrocatalysts. The enhancement of activities arise from either light-excited hot electrons/carriers or photothermy, while the integrating of two action mechanisms is rarely reported. Herein, we present a synergetic effect between light-excited carriers and photothermy to enhance electrocatalytic HER activities of a Co/CoO heterostructured ultrathin nanosheet array supported on Ni foam (denoted as Co/CoO-NF). After exposure to light irradiation, the overpotential at 1...

Boosting Electrocatalytic Hydrogen-evolving Activity of Co/CoO Heterostructured Nanosheets via Coupling Photogenerated Carriers with Photothermy

A photothermal effect strategy to combine the model thermal material, namely, reduced graphene oxide with active species (palladium) was developed to greatly improve the activity and stability of ethanol electrooxidation reaction (EOR). The improvement can be ascribed to both accelerated reaction kinetics of EOR and promoted desorption of the toxic reaction intermediate COads from active palladium caused by the efficient light absorption and subsequent conversion to thermy of reduced graphene oxide. Additionally, this photothermally enhanced strategy was found to be suitable for electrooxidation reactions of other alcohols (e.g., ethylene glycol and glycerol).

Yongmeng Wu

Papers

Selective Transfer Semihydrogenation of Alkynes with H2O (D2O) as the H (D) Source over a Pd‐P Cathode

Converting copper sulfide to copper with surface sulfur for electrocatalytic alkyne semi-hydrogenation with water.

Field-induced reagent concentration and sulfur adsorption enable efficient electrocatalytic semihydrogenation of alkynes

Boosting Electrocatalytic Hydrogen-evolving Activity of Co/CoO Heterostructured Nanosheets via Coupling Photogenerated Carriers with Photothermy

Boosting ethanol electrooxidation via photothermal effect over palladium/reduced graphene oxide