Nanometer-sized electrodes differ greatly from the corresponding bulk electrodes in electrochemical thermodynamics, which is determined by the size and morphology of nanoparticles that constructing the electrodes. However, the influence of size and morphology on the electrochemical thermodynamics remains vague. Herein, the relations of the electrode potential; the temperature coefficient of electrode potential; and the equilibrium constant, thermodynamic properties, and reversible heat of reaction of nanoelectrodes to size and morphology of nanoparticles were systematically deduced. Experimentally, different sizes of nano-silver with morphologies of sphere, wire, and cube were prepared, characterized, and made into nanoelectrodes. And then, the size and morphology-dependent electrochemical thermodynamics of the nanoelectrodes were obtained. Experimental results agree with the theoretical predictions, indicating that with the decrease of particle size, the electrode potential and the reaction equilibrium constant decrease, but the temperature coefficient, the thermodynamic properties, and reversible heat of reaction increase. Furthermore, linear dependences of these electrochemical properties on inverse particle size were confirmed within the experimental size range. At the same equivalent size, the order of size of the electrode potential is E(wire) > E(sphere) > E(cube), while the temperature coefficient and the thermodynamic properties of reaction are opposite. These findings provide important guidance and basis for the design and preparation of highly sensitive electrochemical sensors and chemical cells with high electromotive force and large capacity, and for the electrochemical catalysis and electrochemical corrosion protection.

纳米级电极在电化学热力学上与相应的体电极有很大不同，电化学热力学由构成电极的纳米粒子的尺寸和形态决定。然而，尺寸和形态对电化学热力学的影响仍然模糊。此处，电极电位的关系；电极电位的温度系数；并系统推导了纳米电极的平衡常数，热力学性质和反应可逆性对纳米粒子的尺寸和形貌的影响。实验上，制备，表征和表征了具有球形，金属丝和立方体形貌的不同尺寸的纳米银，并将其制成纳米电极。然后，获得了纳米电极的尺寸和与形态有关的电化学热力学。实验结果与理论预测相符，表明随着粒径的减小，电极电势和反应平衡常数降低，但温度系数，热力学性质和反应可逆热增加。此外，在实验尺寸范围内证实了这些电化学性质对反向粒径的线性依赖性。在相同的等效尺寸下，电极电位的尺寸顺序为 在实验尺寸范围内，证实了这些电化学性质对反粒度的线性依赖性。在相同的等效尺寸下，电极电位的尺寸顺序为 在实验尺寸范围内，证实了这些电化学性质对反粒度的线性依赖性。在相同的等效尺寸下，电极电位的尺寸顺序为E（金属丝）>  E（球体）>  E（立方体），而温度系数和反应的热力学性质相反。这些发现为设计和制备具有高电动势和大容量的高灵敏度电化学传感器和化学电池，以及为电化学催化和电化学腐蚀防护提供了重要的指导和基础。