Calcium oxalate (CaOx) crystallization under laminar flow conditions, relevant for kidney stone formation, was studied in a microfluidic device simulating the geometry of kidney collecting ducts. In a typical microfluidic experiment, two reactive solutions with designated concentrations of calcium (Ca) and oxalate (Ox) ions were brought into contact in a microfluidic channel to create a laminar co-current flow of the two streams. As the streams flow co-currently in the channel, diffusion takes place between the two streams across the channel width, resulting in reactive crystallization leading to CaOx nucleation and growth of CaOx crystals along the mixing front. We studied the growth of these crystals in artificial urine as a function of the fluid flow rate in the channel, the molar ratio of Ca : Ox in the medium and the presence of an organic protein, osteopontin (OPN), known to inhibit the growth of CaOx crystals. Three different flow velocities at a fixed molar ratio of Ca : Ox = 7.5 and four molar ratios of Ca : Ox at a fixed mean flow velocity of 0.035 m s−1 were tested. Lastly, three additive OPN concentrations were evaluated: 2.4 × 10−8 mol m−3, 6 × 10−8 mol m−3 and 8.4 × 10−8 mol m−3. The mean flow velocity did not alter the crystal growth of CaOx in the studied range, whereas altering the molar ratio of Ca : Ox had a high impact on the growth rate. In addition, the type of pseudopolymorph which nucleated appears to depend strongly on the molar ratio. At a low Ca : Ox ratio, both calcium oxalate monohydrate (COM) and calcium oxalate dihydrate (COD) nucleated simultaneously and the growth of the two pseudopolymorphic forms of CaOx crystals was observed. The lowest applied OPN concentration decreased the growth rate of COD, while higher concentrations of OPN slowed down the nucleation kinetics to a point that it completely inhibited the formation of any CaOx crystal in artificial urine within the investigated timeframe. COD was seen under all the conditions investigated, whilst COM was seen in experiments for Ca : Ox molar ratio values between 5 and 6. Our results were rationalized using finite element simulations supported by solution chemistry modelling.@en

Supported metal catalysts have shown to be efficient for CO ₂ conversion due to their multifunctionality and high stability. Herein, we have combined density functional theory calculations with microkinetic modeling to investigate the catalytic reaction mechanisms of CO ₂ hydrogenation to CH ₃OH over a recently reported catalyst of Cd ₄/TiO ₂. Calculations reveal that the metal-oxide interface is the active center for CO ₂ hydrogenation and methanol formation via the formate pathway dominates over the reverse water-gas shift (RWGS) pathway. Microkinetic modeling demonstrated that formate species on the surface of Cd ₄/TiO ₂ is the relevant intermediate for the production of CH ₃OH, and CH ₂O ^# formation is the rate-determining step. These findings demonstrate the crucial role of the Cd-TiO ₂ interface for controlling the CO ₂ reduction reactivity and CH ₃OH selectivity.

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