Liming Zhang

Electrochemical nitrate reduction reaction (eNO3RR) to ammonia (NH3) provides a sustainable route for both NH3 synthesis and nitrate pollutant remediation under ambient conditions. However, the development of efficient catalysts remains challenging due to the complex multielectron reaction pathways and the structural instability of active sites under strongly reducing potentials. Molecular catalysts such as metal phthalocyanines offer well-defined coordination environments for nitrate activation, yet they often suffer from aggregation and irreversible reconstruction during electrocatalysis. Here we report a graphdiyne/graphene (GDY/G) nanostructure-supported molecular catalyst that stabilizes copper phthalocyanine (CuPc) for efficient electrochemical nitrate reduction to NH3. Structural characterizations reveal that the GDY layer enables strong interfacial coupling with CuPc, suppressing molecular aggregation and enhancing catalyst dispersion. At −0.70 V vs RHE, the CuPc/GDY/G catalyst achieves a high NH3 Faradaic efficiency of ∼84% and an exceptional NH3 production rate of 1158 mmol·gcat–1·h–1, markedly outperforming the CuPc/graphene counterpart. Density functional theory calculations show that GDY induces charge redistribution and increases the migration energy barrier of the Cu center, thereby preventing catalyst reconstruction and optimizing the reaction energy landscape. This work demonstrates that carbon-supported nanostructure interfaces can stabilize molecular catalysts under electrochemical conditions and provides a general strategy for designing robust catalysts for nitrate-to-NH3 conversion.

The electrochemical reduction of carbon dioxide (CO2) to multicarbon (C2+) products offers a sustainable strategy for carbon utilization, but the selective formation of target C2+ species remains challenging due to competitive reaction pathways. In this study, we design phase-separated Au–Cu biphasic heterostructures by assembling Au nanoparticles onto Cu nanowires through 4,4′-bipyridine linkers, creating a tunable tandem catalytic interface. Electrochemical tests demonstrate that Au loading regulates C2+ selectivity, where Au1Cu10 predominantly produces ethylene (C2H4) and Au1Cu5 favors ethanol (C2H5OH) formation. Operando spectroelectrochemical measurements and finite-element simulations reveal that modulating the surface density of Au nanoparticles controls the *CO concentration near Cu sites, dictating the reaction pathway. Moderate *CO coverage favors the *OCCHO pathway toward C2H4, whereas high *CO accumulation promotes the *OCCOH pathway leading to C2H5OH. Density functional theory calculations further confirm that *CO coverage modulates the thermodynamic preference for carbon–carbon coupling intermediates. This work establishes a mechanistic link between interfacial *CO availability and C2+ selectivity, offering new design principles for engineered tandem electrocatalysts in CO2 conversion.

Understanding the correlation between surface catalytic motifs and electrochemical reaction pathways is crucial for the rational design of high‐performance electrocatalysts, yet remains hindered by the dynamic reconfiguration of active sites under operating conditions. In this study, we establish a tunable platform based on a series of Cu‐based perovskite oxides with systematically varied A‐site cations to investigate how A‐site chemistry regulates the structural dynamics of Cu and its interplay with the carbon monoxide reduction (COR) pathway. Operando spectroscopic analyses reveal that those perovskites with alkaline‐earth A‐site cations promote Cu clustering into metallic states, favoring multicarbon product formation. In contrast, rare‐earth A‐site perovskites stabilize surface Cu ⁺ species through strong Cu–O interactions, thereby enhancing the selectivity of methane. Complementary theoretical calculations further demonstrate that the Cu─O bond strength—modulated by A‐site composition—dictates the electrochemical stability of Cu active sites. These findings underscore the pivotal role of local coordination environments in steering catalyst reconstruction and product distribution, and provide guiding principles for A‐site engineering in perovskite‐based COR catalysts.

Understanding the correlation between surface catalytic motifs and electrochemical reaction pathways is crucial for the rational design of high‐performance electrocatalysts, yet remains hindered by the dynamic reconfiguration of active sites under operating conditions. In this study, we establish a tunable platform based on a series of Cu‐based perovskite oxides with systematically varied A‐site cations to investigate how A‐site chemistry regulates the structural dynamics of Cu and its interplay with the carbon monoxide reduction (COR) pathway. Operando spectroscopic analyses reveal that those perovskites with alkaline‐earth A‐site cations promote Cu clustering into metallic states, favoring multicarbon product formation. In contrast, rare‐earth A‐site perovskites stabilize surface Cu ⁺ species through strong Cu–O interactions, thereby enhancing the selectivity of methane. Complementary theoretical calculations further demonstrate that the Cu─O bond strength—modulated by A‐site composition—dictates the electrochemical stability of Cu active sites. These findings underscore the pivotal role of local coordination environments in steering catalyst reconstruction and product distribution, and provide guiding principles for A‐site engineering in perovskite‐based COR catalysts.

Understanding the structural dynamics of ligands and their interaction with catalytic centres under reaction conditions remains a fundamental challenge, yet it is essential for catalyst design. Here we reveal an in situ transformation of Ni–Fe hydroxide into a stable superoxo-hydroxide phase, which is accompanied by the formation of lattice O–O (O_latt–O_latt) ligands, as demonstrated using operando ¹⁸O-labelling spectroelectrochemistry and machine-learning-assisted global optimization. By correlating the intrinsic activity of Fe with the O_latt–O_latt concentration across a series of Fe-incorporated transition-metal hydroxides and oxides, we demonstrate that O_latt–O_latt triggers Fe activation for oxygen evolution electrocatalysis—a finding further supported by first-principles calculations. Oxygen production proceeds via an adsorbate evolution mechanism, and the enhanced reaction kinetics stem from the lowered activation energy at surface Fe sites in the newly formed superoxo-hydroxide structure. This work offers a strategic framework for designing high-performance Fe-incorporated electrocatalysts and underscores the pivotal role of ligand dynamics in activating catalytic centres.