The power of Fourier-transformed large amplitude alternating current voltammetry (FTACV) has been applied to parameterize the reduction of the phosphotungstate [PW₁₁O₃₉{Sn(C₆H₄)C≡C(C₆H₄)(N₃C₄H₁₀)}]^4– polyoxometalate (POM) (K^W_Sn[N₃C₄H₁₀]^{4–/5–/6–} processes) at glassy carbon (GC), gold (Au), and platinum (Pt) electrodes as well as its GC surface-confined K^W_Sn[−]^4–-grafted diazonium derivative in acetonitrile (0.10 M [n-Bu₄N][PF₆]). The thermodynamics (E⁰) and heterogeneous electron-transfer kinetics (k⁰ and α) were estimated using the Butler–Volmer relationship. FTACV provides access to significantly more detailed mechanistic information related to nonconformance to the theory than widely used DC voltammetric methods, especially with the more intricate surface-confined electrochemistry. Parameterization, the level of agreement, and systematic variations between experimental and simulated data were established by both an experimenter-controlled heuristic method and by a computationally efficient data optimization approach that employed parameter space searches restricted in scope by knowledge of the heuristically based estimations. The first electron transfer process for both acetonitrile-soluble K^W_Sn[N₃C₄H₁₀]^4– and surface-confined K^W_Sn[−]^4– is always significantly faster than the second. The electrode dependence order is k_GC⁰ > k_Au⁰ > k_Pt⁰ for the K^W_Sn[N₃C₄H₁₀]^4–/5– process. The relatively slower electrode kinetics found for reduction of K^W_Sn[N₃C₄H₁₀]^4– as compared to some other monomeric Keggin POMs may be due to the long organic chain hindering the approach of the POM to the electrode surface, although differences in ion-pairing and other factors also may play a role. Subtle, but systematic, differences identified in comparisons of experimental and simulated voltammetry give rise to apparently data analysis method dependent parameterization and are discussed in terms of nuances not accommodated in the modeling. In the solution-phase voltammetry, data obtained by an electrochemical quartz crystal microbalance and other techniques are consistent with solid adhering to and modifying the electrode surface following reduction of K^W_Sn[N₃C₄H₁₀]^4– to K^W_Sn[N₃C₄H₁₀]^5–. Kinetic and thermodynamic dispersions present in the heterogeneous K^W_Sn[−]^4–-grafted electrode are probable causes of nonideality detected in the surface-confined voltammetry of this material. Thus, FTACV gives valuable insights into what is needed to provide a more realistic description of the polyoxometalate/electrode interface in polyoxometalate electrochemistry by revealing subtle nuances that are often overlooked.

中文翻译：

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伏安还原[ n -Bu ₄ N] ₄ [PW ₁₁ O ₃₉ {Sn（C ₆ H ₄）C≡C（C ₆ H ₄）（N ₃ C ₄）的伏安降低与热力学，电极动力学和机理的细化H ₁₀ }}]和表面受限的重氮衍生物

傅里叶变换大振幅交流伏安（FTACV）的功率已被用于参数化磷钨酸盐[PW ₁₁ O ₃₉ {Sn（C ₆ H ₄）C≡C（C ₆ H ₄）（N ₃ C ₄ H ₁₀）}] ^4–多金属氧酸盐（POM）（K ^W _Sn [N ₃ C ₄ H ₁₀ ] ^{4– / 5– / 6–}工艺）在玻璃碳（GC），金（Au）和铂（Pt ）电极及其GC表面限制的K ^W _Sn [−] ^4–乙腈中接枝重氮鎓衍生物（0.10 M [ n -Bu ₄ N] [PF ₆ ]）。热力学（E ⁰）和异质电子传递动力学（k ⁰和（α）是使用Butler-Volmer关系估算的。与广泛使用的直流伏安法相比，FTACV可以访问与该理论不符相关的更为详细的机械信息，尤其是在表面约束电化学更为复杂的情况下。通过实验者控制的启发式方法和计算有效的数据优化方法（通过采用基于启发式估计的知识限制范围的参数空间搜索），可以建立实验数据和仿真数据之间的参数化，一致性程度和系统差异。乙腈可溶的K ^W _Sn [N ₃ C ₄ H ₁₀ ]的第一电子转移过程^{4 –}和表面受限的K ^W _Sn [−] ⁴ –总是比第二个要快得多。对于K ^W _Sn [N ₃ C ₄ H ₁₀ ] ^{4– / 5–}过程，电极依赖性顺序为k _GC ⁰ > k _Au ⁰ > k _Pt ⁰。发现减少K ^W _Sn [N ₃ C ₄ H ₁₀ ] ^4–的电极动力学相对较慢与其他一些单体Keggin POM相比，可能是由于较长的有机链阻碍了POM接近电极表面，尽管离子对和其他因素的差异也可能起一定作用。在实验伏安法和模拟伏安法的比较中发现的细微但系统的差异，显然导致了数据分析方法所依赖的参数化，并根据模型中未包含的细微差别进行了讨论。在溶液相伏安法中，通过电化学石英晶体微量天平和其他技术获得的数据与固体附着并在还原K ^W _Sn [N ₃ C ₄ H ₁₀ ] ^4–时修饰电极表面一致。至K ^W _Sn [N ₃ C ₄ H ₁₀ ] ^5–。存在于异质K ^W _Sn [-] ^4-接枝电极中的动力学和热力学分散是在这种材料的表面受限伏安法中检测到不理想的可能原因。因此，FTACV通过揭示通常被忽略的细微差别，提供了有价值的见解，以提供对多金属氧酸盐/电化学中的多金属氧酸盐/电极界面进行更现实的描述所需的内容。