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Cations play a crucial role in electrocatalytic reduction of CO₂ and CO to fuels and chemicals, influencing activity and selectivity. This Review explores their effects as indirect mediators, energetic modulators and electron-transfer participants, highlighting key mechanistic insights and knowledge gaps.

Electrochemical interfaces play a crucial role in governing electrode-mediated electron transfer processes, but elucidating the complex effects of the microenvironment remains challenging. Now it has been shown that the Marcus–Hush–Chidsey theory can be used to systematically analyse cation effects on the Au-catalysed CO₂ reduction reaction with experimentally accessible variables.

Herbivory has evolved multiple times across mammals. This study investigates the evolutionary adaptation of the enzyme alanine:glyoxylate aminotransferase (AGT) in mammals and finds AGT’s peroxisomal targeting efficiency, driven by the PTS1 motif, plays a crucial role in adapting to plant-based diets.

The mechanism of electrocatalytic CO/CO₂ reduction on Cu surfaces is complex and its various mechanisms remain under debate, including the important role of cations in the electrolyte. Here the authors quantitatively determine the impact of alkali cations on the thermodynamics of CO adsorption under electrochemical conditions and the activation parameters of the rate-determining step.

The authors demonstrate a TEMPO-mediated urotropine electrosynthesis that is accelerated by defective carbon, as the vacancy defects transfer the oxidation of TEMPOH from a sluggish outer sphere process into a rapid inner sphere mechanism via adsorption.

An artificial nerve that is based on a vertical n-type organic electrochemical transistor with a gradient-intermixed bicontinuous structure can operate at high frequencies and mimic basic conditioned reflex behaviour in animals.

Quantifying the individual capacitance contributions of in-pore ions during charging remains a challenge. Here the authors design silica-grafted ionic liquids to reveal the charging behaviors of cations and anions separately, providing fresh insight into the storage mechanism of supercapacitors.

Electrosynthesis of n-propanol from CO has been limited by poor selectivity and low product concentration. Here a Sn–Cu catalyst/carbon/ionomer heterojunction is prepared where the adjacent atomic active sites favour the coupling of C₁ and C₂ intermediates to C₃ product with 47% Faradaic efficiency and the reversal of electro-osmotic drag concentrates the product to 30 wt%.

High-pressure infrared spectroscopy shows concentrated cations suppress CO adsorption. Here the authors report two electrochemical interfaces forming distinct double layer structures and reaction rates at elevating pressure and various potentials.

The electrocatalytic NO reduction reaction enables sustainable NH₃ synthesis and NO removal but faces challenges in achieving industrial-level efficiency and durability. Here the authors present an in situ-formed copper nanowire array monolithic electrode integrated into a pressurized electrolyzer for stable ammonia electrosynthesis at around 1000 mA cm^–2 for 100 h.

Commercially viable catalytic CO₂ electroreduction to CO would enable many green technologies, yet it is impeded by the initial hydrogenation step of CO₂. Here, the authors report Ni-Cd dual atom catalysts with complementary properties of favorable adsorption of CO₂ and H to overcome this barrier.

The activation of light alkanes under mild conditions is a challenging task. Now the conversion of alkanes into the corresponding olefins and oxygenates is achieved in solution using Cu powder at ambient temperature and pressure.

Electrokinetic results are key to understanding the mechanisms in electrochemical CO reduction reaction. Here, the authors determine mass transport free kinetics using a gas-diffusion electrode and identified dependence of copper surface speciation on the electrolyte pH using in situ surface enhanced spectroscopies.

The activation of propane at mild conditions is challenging. Now a microfluidic reaction system with a Cu microtube serving as both the catalyst and the microchannel reactor can selectively convert propane to propylene at room temperature and ambient pressure.

While the electrochemical conversion of CO₂ to highly reduced products is unique to copper, there are still gaps in understanding copper catalysts’ efficacy. Here, authors find that co-electrolysis of CO₂ with O₂ can enhance copper’s catalytic activities.

While homodimeric prodrug assemblies can improve drug loading and limit toxicity in cancer therapy, bioactivation within the target site is limited. Here, the authors introduce a hybrid chalcogen bond linker to a docetaxel dimeric prodrug nanoassembly and demonstrate its improved selfassembly, redox-responsivity and antitumor efficacy.

Here, the authors demonstrate a Cu-based catalyst with Cu–Ag interfacial sites, which favor oxygenate over alcohol production in CO₂ electroreduction. Near 80% selectivity for multi-carbon liquid products in a 100 cm² membrane electrode assembly electrolyzer is exhibited over 100 h.

Developing operando spectroscopic techniques with high sensitivity and reproducibility is of great importance for mechanistic investigations of surface-mediated electrochemical reactions. Here the authors study reaction mechanism of CO electroreduction using highly ordered gold superlattices as substrate for surface-enhanced infrared absorption spectroscopy.

Photoelectrochemical water splitting affords an integrated approach for converting light to fuel, but devices typically suffer poor activities and stabilities. Here, authors incorporate black phosphorene into bismuth vanadate photoanodes to boost hole extraction and device lifetimes.

Anchored single-atom catalysts have recently been shown to be very active for various processes, however, a catalyst that features two adjacent copper atoms—which we call an atom-pair catalyst—is now reported. The Cu₁⁰–Cu₁^x+ pair structures work together to carry out the critical bimolecular step in CO₂ reduction.

The exterior layers of mollusk shells are prismatic in nature, endowing them with stiffness and wear resistance. Inspired by these biominerals, here, Jiang and colleagues grow structurally similar prismatic-type CaCO₃ thin films with comparable stiffness and hardness.

The kinetic parameters in heterogeneous catalysis are informative in a mechanistic study. Here, the authors show the correlation between the coordination environment of isolated boron sites and the kinetics of oxidative dehydrogenation of propane.

Efficient oxygen evolution reaction electrocatalysts are essential for sustainable clean energy conversion. Here, the authors propose a Co-Fe dual-site to facilitate the ferromagnetic O-O bond coupling to achieve a great balance between activity and stability.

It is challenging to develop high-activity and durable catalysts for both ethanol oxidation reaction on the anode and oxygen reduction reaction on the cathode. Here in this work, authors proposed Pd/Co@N-C catalyst as a model to synergistically maximize the usage of catalyst nanoparticles and active interfaces for direct ethanol fuel cells.

Liquid phase reactions mediated by solid catalysts occur in the presence of solvents whose role needs to be understood. The authors use attenuated total reflection infrared spectroscopy to measure liquid-phase pyridine adsorption isotherms in zeolites, elucidating the effect of coadsorbed solvents on the interactions.

This paper demonstrates a highly efficient on-chip solar cell design that achieves 25.79% photoelectric conversion efficiency by reducing electrode shading through innovative center electrodes and high-doping interconnections. The results support the development of stable, self-powered microsensors for Internet of Things(IoT) applications.

Genetics and transcriptomics reveal shared mechanisms of psychiatric and gastrointestinal disorders, highlighting neurological pathways and pleiotropic loci. Genes BSN, CELF4, NRXN1 regulate gut-brain axis, revealing potential therapeutic targets.