Yang Tian

In situ measurements reveal that Zn and Pd work synergistically to regulate surface OH ⁻ enrichment and the adsorption of reactants on ZnPd-NiOOH, thereby enhancing the electro-oxidation of BDO to SA for plastic upcycling.

Asymmetric Fe–O–Ni coupling in NiFe-MOF/BiVO ₄ induces a Ni d _z ² spin-state transition that facilitates *OOH desorption, boosting the photocurrent to 6.0 mA cm ⁻² at 1.23 V vs. RHE.

For valuable ammonia synthesis and green nitrogen recycling, electrocatalytic nitrate reduction reaction (NO ₃ RR) presents a sustainable alternative to the conventional Haber–Bosch process. The NO ₃ RR involves intricate, multi-step proton-coupled electron transfers (PCET) featuring multiple nitrogen-oxygen intermediates and reaction branches. Unveiling this complex reaction library is crucial for rational tailoring of NO ₃ RR for improved practical application, yet it remains a formidable challenge. Herein we present an in situ ultramicroelectrode-hyphenated mass spectrometry technique to systematically investigate the dynamic electrocatalytic NO ₃ RR, using a cobalt-based molecular catalyst as a model system, and to decipher its mechanistic library under complex reaction environments (potential- and pH-dependent). Several key short-lived CoNO _x H _y intermediates were directly tracked and identified, experimentally revealing that the overall catalytic pathway of NO ₃ RR proceeds through the intermediary [LCo-NO ₃ ]→[LCo-NO ₃ H] ⁺ →[LCo-NO ₂ ] ⁺ → [LCo-NO ₂ H] ⁺ → [LCo-NO] ⁺ → [LCo-NHOH] ⁺ → [LCo-NH] ⁺ to produce NH ₃ , which were further validated by isotopic ¹⁵ N-labeling and collision-induced dissociation experiments. Combining theoretical simulations, a complete PCET-based mechanistic pathway was elucidated and distinguished from competing hydrogenation–deoxygenation mechanisms. Notably, a systematically interconnected electrochemical mechanistic library for NO ₃ RR, visualized through heat maps, was constructed to illustrate intermediate selectivity across a broad potential-pH space. This platform underscores the promising potential of navigating the pathway prediction and regulation of complex reaction environments, thereby advancing the mechanistic understanding of NO ₃ RR and other complicated electrocatalytic processes.

Active oxygen radicals (OH*/O*/OOH*) generated from oxygen evolution reaction (OER) play a crucial role in facilitating the electrooxidation of organic compounds into high value-added chemicals. However, constructing atomically precise active sites with a specific function to catalyze water-coupled electrooxidation reactions in a tandem system still confronts a great challenge. Herein, we propose a novel water-participating benzyl alcohol electrooxidation tandem process by constructing homogeneous isolated Fe-Pt dual-sites on CoOOH nanosheet arrays (FePt DAC). The Fe and Pt dual atomic sites synergistically deliver excellent benzyl alcohol oxidation reaction activity with high current density of 1500 mA cm^-2 at a low potential of 1.49 V (vs RHE) and remarkable long-term durability without obvious attenuation after 530 h operation. In-situ Fourier transform infrared spectroscopy, isotopic tracing experiment and detailed theoretical calculations further reveal the tandem mechanism, in which the in-situ generated O* species on the Fe site through OER process serve as key intermediates that bridge the subsequent electrochemical benzyl alcohol oxidation on neighboring Pt site. This coupled oxidation mechanism turns competitive OER process into mutual benefits, and provides insights to achieve directional transformation of chemical bonds via construction of collaborative dual atomic sites.

Zero‐dimensional (0D) organic metal halides (OIMHs) with room‐temperature phosphorescent (RTP) properties have aroused great research enthusiasm due to their long lifetime of triplet excitons and environment stability. Despite extensive research on the RTP emission of OIMHs in different metal ions, there has been limited reporting on the excellent luminescent properties of triplet excitons originating from organic ligands via metallic halide modulation, although they have intriguing luminescent properties. Here, piperonylamine (piperA) is taken as organic cations and two new OIMHs are synthesized, (piperA) ₃ ClSbCl ₅ and (piperA) ₃ ClInCl ₅ ·H ₂ O, with differently enhanced RTP emission compared with (piperA)Cl ligand. Structural and photophysical studies reveal that the increased RTP emission is due to the enhanced π–π stackings between the adjacent piperA ligands in (piperA) ₃ ClSbCl ₅ and (piperA) ₃ ClInCl ₅ ·H ₂ O. Mechanism analysis demonstrates that the diverse stacking arrangements of crystal structure result in distinct energy transfer pathways, potentially accounting for the varying degrees of enhancement in phosphorescent lifetime. This work developed a method for regulating the RTP of organic ligands in OIMH using metal ions to achieve long RTP emission, providing a new approach for designing ultra‐long RTP emission materials.

Photoelectrochemical (PEC) water splitting has great potential for solar energy conversion to hydrogen. However, the slow charge transfer in the photoanodes remains a core issue limiting the PEC performance. In this study, we address this issue by constructing a single atom bridge (SAB) Cu-O₂N at the interface between BiVO₄ and covalent organic framework (COF) layer. X-ray absorption fine spectra and theoretical calculations demonstrate that the single atom bridge is formed by the interfacial coordination reconstruction between BiVO₄ and COF layers and create intermediate electronic states to facilitate the hole extraction. As a result, the SAB photoanode exhibits enhanced PEC water oxidation performance. Specifically, it achieves a photocurrent density of 4.84 mA cm^-2 at 1.23 V vs. RHE in PEC simulant seawater splitting with a cocatalyst, higher than nearly all the previously reported BiVO₄-based photoanodes. This work offers valuable insights into fast charge transfer in PEC systems and proposes a promising strategy for designing efficient photoelectrodes for seawater splitting.

Photoelectrochemical (PEC) water splitting for hydrogen generation holds immense potential for addressing environmental and energy crises. Tailoring non‐covalent interaction via a single atom is anticipated to realize prominent hole extracting facilitating PEC performance, but it has never been reported. In this study, single atom Co‐N₄ is coordinated with 5‐fluoroanthranilic acid (FAA) molecules, then used as a non‐covalent hole‐extracting layer on a BiVO₄ substrate. Experiments including X‐ray absorption fine spectra, Kelvin probe force microscopy, transient absorption, and theoretical calculation demonstrate the FAA coordination alters the local configuration of the central Co atom, adjusting the interfacial non‐covalent interaction, thereby reducing the barrier of charge transfer between BiVO₄ and the hole‐extracting layer. Consequently, photogenerated carriers are more effectively separated, and the PEC water oxidation performance is significantly enhanced with the photocurrent density of 5.47 mA cm⁻² at 1.23 V versus RHE, much higher than those of previously reported BiVO₄ photoanodes composited with porphyrin‐based compounds. Experiments and theoretical simulation confirm that the boosted PEC performance originates from exceptional interfacial charge transfer rather than surface catalysis dynamic. This study provides an efficient strategy for tailoring non‐covalent interaction by regulating single‐atom coordination and promoting hole extract to boost PEC water oxidation activity.

In this review, we present a summary of recent research on the regulation of triplet-state emissions in non-lead organic–inorganic metal halides. We focus on exploring the internal and external factors influencing the triplet-states emission.