Structural Fusion‐Induced Activity Suppression in Copper Nanoclusters for Electrocatalytic Nitrate Reduction

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Angewandte Chemie Int Ed, Wiley-VCH

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Angewandte Chemie International Edition, EarlyView.

An anion‐templated fusion strategy enables the precise structural evolution of copper nanoclusters, yielding a well‐defined Cu40 supercluster. Electrocatalytic nitrate‐reduction studies show that structural fusion diminishes the catalytic activity of the clusters, exhibiting anomalous anti‐emergent behavior. ABSTRACT Understanding how structural evolution influences catalytic behavior is a central challenge in chemistry. We establish an atomically precise platform to directly probe the catalytic consequences of structural fusion in copper nanoclusters and uncover a counterintuitive anti‐emergent phenomenon, wherein increased structural complexity leads to suppressed activity. By integrating thiacalix[4]arene with an ortho‐hydroxyl‐substituted alkynyl ligand, we enable the in situ generation and directional templating of C22− dianions, achieving controlled fusion of two Cu17 units into a well‐defined supercluster, {(C2)6@Na2Cu40(TC4A)6(3‐HOhexC≡C)6} (Cu40). Precise regulation of the hydroxyl position allows selective isolation of the monomeric counterpart {NaCu17(TC4A)3(6‐HOhexC≡C)6} (Cu17), providing a closely matched model pair to disentangle fusion effects. The generality of this C22−‐templated fusion pathway is further supported by the isolation of Cu22 and Cu43 clusters. Comparative electrocatalytic analysis shows that, despite similar topological architectures, Cu40 exhibits markedly inferior nitrate‐reduction activity relative to the Cu17 and Cu22 monomers. Notably, Cu17 delivers an optimal NH3 Faradaic efficiency of 98.45% with a production rate of 2.91 mol·h−1·g−1 at −1.0 V. In situ spectroscopic experiments combined with DFT calculations reveal that fusion preserves the intrinsic nature of Cu active sites but reduces surface accessibility and perturbs local electronic environments, thereby suppressing interfacial *H formation and hindering hydrogenation of *NO intermediates.

An anion-templated fusion strategy enables the precise structural evolution of copper nanoclusters, yielding a well-defined Cu₄₀ supercluster. Electrocatalytic nitrate-reduction studies show that structural fusion diminishes the catalytic activity of the clusters, exhibiting anomalous anti-emergent behavior.

Understanding how structural evolution influences catalytic behavior is a central challenge in chemistry. We establish an atomically precise platform to directly probe the catalytic consequences of structural fusion in copper nanoclusters and uncover a counterintuitive anti-emergent phenomenon, wherein increased structural complexity leads to suppressed activity. By integrating thiacalix[4]arene with an ortho-hydroxyl-substituted alkynyl ligand, we enable the in situ generation and directional templating of C₂ ^{2 −} dianions, achieving controlled fusion of two Cu₁₇ units into a well-defined supercluster, {(C₂)₆@Na₂Cu₄₀(TC4A)₆(3-HOhexC≡C)₆} (Cu₄₀ ). Precise regulation of the hydroxyl position allows selective isolation of the monomeric counterpart {NaCu₁₇(TC4A)₃(6-HOhexC≡C)₆} (Cu₁₇ ), providing a closely matched model pair to disentangle fusion effects. The generality of this C₂ ^{2 −}-templated fusion pathway is further supported by the isolation of Cu₂₂ and Cu₄₃ clusters. Comparative electrocatalytic analysis shows that, despite similar topological architectures, Cu₄₀ exhibits markedly inferior nitrate-reduction activity relative to the Cu₁₇ and Cu₂₂ monomers. Notably, Cu₁₇ delivers an optimal NH₃ Faradaic efficiency of 98.45% with a production rate of 2.91 mol·h⁻¹·g⁻¹ at −1.0 V. In situ spectroscopic experiments combined with DFT calculations reveal that fusion preserves the intrinsic nature of Cu active sites but reduces surface accessibility and perturbs local electronic environments, thereby suppressing interfacial *H formation and hindering hydrogenation of *NO intermediates.

Xin‐Yu Chen, Ya‐Qi Li, Xin‐Yu Bai, Dang‐Dang Ding, Xin‐Yan Chi, Wei‐Qiang Zhang, Jun Yan, Tian‐Fu Liu, Yong Pei, Chao Liu

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