Investigating the Role of Copper Oxide in Electrochemical CO2 Reduction in Real Time.

Copper oxides have been of considerable interest as electrocatalysts for CO2 reduction (CO2R) in aqueous electrolytes. However, their role as an active catalyst in reducing the required overpotential and improving the selectivity of reaction compared with that of polycrystalline copper remains controversial. Here, we introduce the use of selected-ion flow tube mass spectrometry, in concert with chronopotentiometry, in situ Raman spectroscopy, and computational modeling, to investigate CO2R on Cu2O nanoneedles, Cu2O nanocrystals, and Cu2O nanoparticles. We show experimentally that the selective formation of gaseous C2 products (i.e., ethylene) in CO2R is preceded by the reduction of the copper oxide (Cu2OR) surface to metallic copper. On the basis of density functional theory modeling, CO2R products are not formed as long as Cu2O is present at the surface because Cu2OR is kinetically and energetically more favorable than CO2R.

Dramatic Enhancement in Photoresponse of ß-In2S3 through Suppression of Dark Conductivity by Synthetic Control of Defect-Induced Carrier Compensation.

We report on the synthesis of dense and faceted indium sulfide (ß-In2S3) nano-octahedron films on fluorine-doped tin oxide-coated glass by the hydrothermal method and their photoresponse properties in a flip chip device configuration. We have examined the temporal evolution of the phase constitution, morphology, and optoelectronic properties for films obtained after growth interruption at specific intervals. It is noted that, initially, an In(OH)3 film forms, which is gradually transformed to the ß-In2S3 phase over time. In the case of the film wherein most, but not all, of In(OH)3 is consumed, an exceptionally large photoresponse (light to dark current ratio) of ∼10(4) and response time(s) (rise/fall) of ∼88/280 ms are realized. This superior performance is attributed to nearly complete carrier compensation achievable in the system under high pressure growth leading to dramatic reduction of dark conductivity. It is argued that the temporally growth-controlled equilibrium between quasi-In interstitials and cation vacancies dictates the optoelectronic properties.

Self-powered UV-vis photodetector based on ZnIn2S4/hydrogel interface.

The photosensing properties of vertically aligned ZnIn2S4 nanopetal films grown hydrothermally on FTO coated glass are examined without and with surface dispensed agarose gel. For the ZnIn2S4 nanopetals photodetector (without gel) there is no photoresponse for zero bias. Most interestingly, with surface dispensation of agarose gel, the hybrid electronic-iontronic interface system shows a strong photoresponse even under zero bias, a highly efficient self-powered UV-visible light photodetector. Indeed, the zero bias ZnIn2S4/gel hybrid photoresponse is a factor of 100 stronger as compared to the response of the only ZnIn2S4 device (at -1.5 V bias) and that too without any significant degradation in response time. The possible operating mechanisms are proposed.

A quasi-liquid iontronic-electronic light-harvesting hybrid photodetector with giant response.

A heterostructure formed by a layer of agarose gel drop-cast on a hydrothermally grown layer of ZnO nanorods on fluorine-doped tin oxide (FTO)-coated glass is examined for photoresponse with a top platinum tip contact. This ionic-gel-based hybrid device shows three orders of magnitude higher photocurrent as compared to the case of bare ZnO nanorods film.