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Abstract This work reports the fabrication of p‐type Si micropillar (MP) substrates decorated with AgxCu100−x bimetallic nanoparticles and their application as photocathodes for CO2 photoelectrochemical reduction. Metal deposition by metal‐assisted chemical etching is chosen as the nanoparticle synthesis method, to explore for the first time its capabilities for 3D structures. It is found to be applicable, allowing a good control of the composition, with nanoparticles distributed along the entire MP, but with a coverage gradient from top to bottom. The AgxCu100−x decorated Si MPs photocathodes show enhanced light trapping compared to flat Si, with 45 % lower reflectance values in the visible and significantly higher catalytic activity, in terms of photocurrent density, overpotential and power savings (4.7 % for Ag50Cu50/Si MPs vs. 3 % for Ag50Cu50/flat‐Si). Si MPs coated with Ag50Cu50 and Ag20Cu80 provide the highest gain in potential (440 and 600 mV vs. bare Si MPs) and an increased selectivity towards high energy density products (i. e., CH4) compared to monometallic photocathodes. These are promising features for efficient light‐driven CO2 conversion. However, a significant metal loss is observed during photoelectrolysis, especially for Cu‐rich compositions. Suggestions to improve the photocathode performance in terms of metal coating homogeneity and catalyst stability are presented.

This article presents a study on Metal-Assisted Chemical Etching (MACE) of silicon in HF-H2O2 using silver nanoparticles as catalysts. Our aim is a better understanding of the process to elaborate new 3D submicrometric surface structures useful for light management. We investigated MACE over the whole range of silicon doping, i.e., p++, p+, p, p−, n, n+, and n++. We discovered that, instead of the well-defined and straight mesopores obtained in p and n-type silicon, in p++ and n++ silicon MACE leads to the formation of cone-shaped macropores filled with porous silicon. We account for the transition between these two pore-formation regimes (straight and cone-shaped pores) by modeling (at equilibrium and under polarization) the Ag/Si/electrolyte (HF) system. The model simulates the system as two nanodiodes in series. We show that delocalized MACE is explained by a large tunnel current contribution for the p-Si/Ag and n-Si/HF diodes under reverse polarization, which increases with the doping level and when the size of the nanocontacts (Ag, HF) decreases. By analogy with the results obtained on heavily doped silicon, we finally present a method to form size-controlled cone-shaped macropores in p silicon with silver nanoparticles. This shape, instead of the usual straight mesopores, is obtained by applying an external anodic polarization during MACE. Two methods are shown to be effective for the control of the macropore cone angle: one by adjusting the potential applied during MACE, the other by changing the H2O2 concentration. Under appropriate etching conditions, the obtained macropores exhibit optical properties (reflectivity ~3 %) similar to that of black silicon.

Nanoporous gold and platinum electrodes are used to pattern n-type silicon by contact etching at the macroscopic scale. This type of electrode has the advantage of forming nanocontacts between silicon, the metal and the electrolyte as in classical metal assisted chemical etching while ensuring electrolyte transport to and from the interface through the electrode. Nanoporous gold electrodes with two types of nanostructures, fine and coarse (average ligament widths of ~30 and 100 nm, respectively) have been elaborated and tested. Patterns consisting in networks of square-based pyramids (10 × 10 μm2 base × 7 μm height) and U-shaped lines (2, 5, and 10 μm width × 10 μm height × 4 μm interspacing) are imprinted by both electrochemical and chemical (HF-H2O2) contact etching. A complete pattern transfer of pyramids is achieved with coarse nanoporous gold in both contact etching modes, at a rate of ~0.35 μm min−1. Under the same etching conditions, U-shaped line were only partially imprinted. The surface state after imprinting presents various defects such as craters, pores or porous silicon. Small walls are sometimes obtained due to imprinting of the details of the coarse gold nanostructure. We establish that np-Au electrodes can be turned into “np-Pt” electrodes by simply sputtering a thin platinum layer (5 nm) on the etching (catalytic) side of the electrode. Imprinting with np Au/Pt slightly improves the pattern transfer resolution. 2D numerical simulations of the valence band modulation at the Au/Si/electrolyte interfaces are carried out to explain the localized aspect of contact etching of n-type silicon with gold and platinum and the different surface state obtained after patterning. They show that n-type silicon in contact with gold or platinum is in inversion regime, with holes under the metal (within 3 nm). Etching under moderate anodic polarization corresponds to a quasi 2D hole transfer over a few nanometers in the inversion layer between adjacent metal and electrolyte contacts and is therefore very localized around metal contacts.

Developing micro- and nanomaterials for environmental pollution remediation is currently a pertinent topic. Among the plethora of strategies, designing supported nanocatalysts for the degradation of pollutants has achieved prominence. In this context, we are addressing one of the UN Sustainable Development Goals by valorizing agrowaste as a source of biochar, which serves as a support for bimetallic nanocatalysts. Herein, olive pit powder particles were impregnated with copper and nickel nitrates and pyrolyzed at 400 °C. The resulting material consists of bimetallic CuNi-decorated biochar. CuNi nanocatalysts were found to be as small as 10 nm and very well dispersed over biochar with zero valent copper and nickel and the formation of copper–nickel solid solutions. The biochar@CuNi (B@CuNi) exhibited typical soft ferromagnet hysteresis loops with zero remanence and zero coercivity. The biochar@CuNi was found to be an efficient catalyst of the reduction in methyl orange (MO) dye, taken as a model pollutant. In sum, the one-pot method devised in this work provides unique CuNi-decorated biochar and broadens the horizons of the emerging topic of biochar-supported nanocatalysts.