Current status of carbon monoxide dehydrogenases (CODH) and their potential for electrochemical applications.

Anthropogenic carbon dioxide (CO2) levels are rising to alarming concentrations in earth's atmosphere, causing adverse effects and global climate changes. In the last century, innovative research on CO2 reduction using chemical, photochemical, electrochemical and enzymatic approaches has been addressed. In particular, natural CO2 conversion serves as a model for many processes and extensive studies on microbes and enzymes regarding redox reactions involving CO2 have already been conducted. In this review we focus on the enzymatic conversion of CO2 to carbon monoxide (CO) as the chemical conversion downstream of CO production render CO particularly attractive as a key intermediate. We briefly discuss the different currently known natural autotrophic CO2 fixation pathways, focusing on the reversible reaction of CO2, two electrons and protons to CO and water, catalyzed by carbon monoxide dehydrogenases (CODHs). We then move on to classify the different type of CODHs, involved catalyzed chemical reactions and coupled metabolisms. Finally, we discuss applications of CODH enzymes in photochemical and electrochemical cells to harness CO2 from the environment transforming it into commodity chemicals.

Stabilizing an ultrathin MoS2 layer during electrocatalytic hydrogen evolution with a crystalline SnO2 underlayer.

Amorphous MoS2 has been investigated abundantly as a catalyst for hydrogen evolution. Not only its performance but also its chemical stability in acidic conditions have been reported widely. However, its adhesion has not been studied systematically in the electrochemical context. The use of MoS2 as a lubricant is not auspicious for this purpose. In this work, we start with a macroporous anodic alumina template as a model support, add an underlayer of SnO2 to provide electrical conduction and adhesion, then provide the catalytically active, amorphous MoS2 material by atomic layer deposition (ALD). The composition, morphology, and crystalline or amorphous character of all layers are confirmed by spectroscopic ellipsometry, X-ray photoelectron spectroscopy, grazing incidence X-ray diffractometry, scanning electron microscopy and energy dispersive X-ray spectroscopy. The electrocatalytic water reduction performance of the macroporous AAO/SnO2/MoS2 electrodes, quantified by voltammetry, steady-state chronoamperometry and electrochemical impedance spectroscopy, is improved by annealing the SnO2 layer prior to MoS2 deposition. Varying the geometric parameters of the electrode composite yields an optimized performance of 10 mA cm-2 at 0.22 V overpotential, with a catalyst loading of 0.16 mg cm-2. The electrode's stability is contingent on SnO2 crystallinity. Amorphous SnO2 allows for a gradual dewetting of the originally continuous MoS2 layer over wide areas. In stark contrast to this, crystalline SnO2 maintains the continuity of MoS2 until at least 0.3 V overpotential.