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            Hypothesis Through a large parameter space, electric fields can tune colloidal interactions and forces leading to diverse static and dynamical structures. So far, however, field-driven interactions have been limited to dipole-dipole and hydrodynamic contributions. Nonetheless, in this work, we propose that under the right conditions, electric fields can also induce interactions based on local chemical fields and diffusiophoretic flows. Experiments Herein, we present a strategy to generate and measure 3D chemical gradients under electric fields. In this approach, faradaic reactions at electrodes induce global pH gradients that drive long-range transport through electrodiffusiophoresis. Simultaneously, the electric field induces local pH gradients by driving the particle's double layer far from equilibrium. Findings As a result, while global pH gradients lead to 2D focusing away from electrodes, local pH gradients induce aggregation in the third dimension. Evidence points to a mechanism of interaction based on diffusiophoresis. Interparticle interactions display a strong dependence on surface chemistry, zeta potential and diameter of particles. Furthermore, pH gradients can be readily tuned by adjusting the voltage and frequency of the electric field. For large Péclet numbers, we observed a collective chemotactic-like collapse of particles. Remarkably, such collapse occurs without reactions at a particle's surface. By mixing particles with different sizes, we also demonstrate, through experiments and Brownian dynamics simulations, the emergence of non-reciprocal interactions, where small particles are more drawn towards large ones.more » « lessFree, publicly-accessible full text available January 1, 2026
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