Accounts of Chemical Research最新文献

By tapping Earth’s most abundant water resource, seawater electrolysis offers a promising route to hydrogen production while reducing reliance on freshwater. However, in natural seawater and at industrial current densities (j), complex ion–catalyst interactions at the interface can accelerate activity decay and undermine long-term durability. On the anode, halide attack dominated by Cl^– can shift selectivity from the oxygen evolution reaction toward the chlorine evolution reaction and trigger the metal-chloride/hydroxide corrosion pathway, causing loss of active sites and poor oxygen selectivity. On the cathode, the local pH increase induced by the hydrogen evolution reaction can drive Mg²⁺/Ca²⁺ precipitation, forming fouling layers that block active sites and hinder continuous operation. Additionally, inadequate control of gas release and the solid–gas interface at industrial j can accelerate bubble-induced mechanical damage to the catalyst layer. In this Account, we summarize our group’s progress in engineering catalyst surfaces and interfaces toward efficient and durable seawater electrolysis.

We begin by outlining anode-focused strategies that improve seawater oxidation activity and halide tolerance. First, anion-species regulation is applied to (1) construct anion-rich surfaces that repel Cl^–, (2) engineer a Lewis-acid-enabled OH^–-enriched microenvironment that favors *OH over Cl^–, and (3) build a high-density negatively charged network that efficiently excludes Cl^– at industrial j. Next, surface coordination regulation is introduced in which strongly chemisorbed molecular regulator tunes the electronic structure of metal centers and reinforces Cl^– repulsion. Subsequently, we design a multidefense architecture that integrates an anion-rich surface and oxygen-intermediate-rich layer within a tip-connected bubble management framework, enabling simultaneous mitigation of chlorine chemistry and mechanical stress at industrial j. On the cathode side, we develop a microscopic bubble/precipitate traffic system (MBPTS) and self-cleaning electrode that control gas and ion transport, continuously remove Mg²⁺/Ca²⁺ deposits, and enable concurrent H₂ production and magnesium recovery. Finally, we outline the remaining limitations and emerging opportunities in seawater electrolysis to inspire next-generation designs for saline electrochemical energy systems and beyond.

Twisted graphene nanoribbons (tw-GNRs), exemplified by helical perylene diimide (hPDI) oligomers and polymers, represent a versatile platform for next-generation organic electronics. Their distinctive architecture features a fused, twisted backbone that simultaneously introduces void space for ion transport while maintaining high electronic conductivity along the graphitic core. This Account details the development of these materials, underpinned by a defect-free polymerization-cyclization synthesis based on perylene tetraester precursors. This robust synthetic route enables the creation of ribbons up to 120 nm long with precise control over molecular length, edge chemistry, and backbone helicity, allowing for a systematic investigation of structure–property relationships.

Leveraging this unique combination of properties, we address key challenges in energy storage, bioelectronics, and chiroptics. In the context of energy storage, we discuss how intermediate-length ribbons strike a structural “sweet spot” that balances the trade-off between electrode insolubility and ion permeability, facilitating ultrafast charging kinetics in lithium and magnesium batteries. Furthermore, we demonstrate how introducing cruciform hinges into the backbone creates an amorphous morphology that resolves the critical “conductivity–hydrophilicity–insolubility” trade-off, enabling high-performance aqueous sodium-ion batteries. In bioelectronics, we describe how modifying the ribbon edges with hydrophilic chains enables high performance and ultrastable n-type organic mixed ionic–electronic conductors (OMIECs) capable of high-fidelity neural recording. Finally, we explore the chiroptical properties of these ribbons, explaining how remote chiral side chains can dynamically induce long-range helical order in the backbone. This structural control allows the materials to function as room-temperature spin filters via the chiral-induced spin selectivity (CISS) effect.

Collectively, these studies illustrate how precise molecular engineering can unlock new functionalities, ranging from dual ion-electron conduction to spin-selective transport, defining a versatile platform for next-generation organic electronics.