Self-assembled monolayers of alkane thiolate and alkane selenolate have been proven to inhibit atmospheric corrosion, but upon prolonged exposure to the important constituents of indoor atmosphere, namely humidified air with formic acid, the protective layer eventually breaks, but the exact reason is not yet clear. In this paper, we report on an XPS study of co-adsorbed formic acid and hexane selenol on a Cu surface. Adsorption of hexane selenol at room temperature breaks the Se-C bond, leaving a monolayer of Se on the surface, whereas adsorption at 140 K leaves a layer of selenolate. Formic acid exposure to the selenolate-Cu surface leads to adsorbed formate on unprotected areas and absorption of formic acid within the alkane chain network. During heating, the formic acid desorbs and the Se-C bond breaks, but formic acid does not accelerate the Se-C scission, which occurs just below room temperature both with and without formic acid. Thus, formic acid alone does not affect the Se-C bond, but its presence may create disorder and open up the alkane carpet for other species. Selenol removes formate and oxide from the surface at room temperature. The Se-C bond breaks and the alkane chain reacts with surface oxygen to form carbon oxides and volatile hydrocarbons.

Salt removal from seawater and brackish water by Capacitive deionization (CDI) is an emerging technology that has a potential to contribute to solving global shortages of freshwater. Upon the application of an external voltage to a pair of nanostructured carbon electrodes, ions are removed by electrosorption in the electrical double layer (EDL) of the capacitor. The physical limitation due to repulsion of co-ions can be reduced using intercalation materials that are less sensitive to ion concentration variations. Herein, we report a hollow-concave high-entropy Prussian blue analogue (HEPBA) enhanced electrodes for superior electrochemical and capacitor performances. The half-cell of hollow-concave HEPBA has a high cycling stability of 1000 cycles at a current density of 1 A g−1. Lower energy consumption for desalination estimated over 90 cycles is due to an enhancement of salt adsorption capacity of HEPBA (∼ 26.2 mg g−1). The observed improvement in the electrochemical property is due to synergistic effects from multi-elemental composition that lead to the high entropy and specific surface area. Hollow-concave HEPBA are structurally stable with negligible changes in the lattice parameters during extensive charging and discharging cycles. This simple method offers an opportunity to modify the structure and morphology of PBAs for real-life applications.

MXene is a promising energy storage material for miniaturized microbatteries and microsupercapacitors (MSCs). Despite its superior electrochemical performance, only a few studies have reported MXene-based ultrahigh-rate (>1000 mV s−1) on-paper MSCs, mainly due to the reduced electrical conductance of MXene films deposited on paper. Herein, ultrahigh-rate metal-free on-paper MSCs based on heterogeneous MXene/poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS)-stack electrodes are fabricated through the combination of direct ink writing and femtosecond laser scribing. With a footprint area of only 20 mm2, the on-paper MSCs exhibit excellent high-rate capacitive behavior with an areal capacitance of 5.7 mF cm−2 and long cycle life (>95% capacitance retention after 10,000 cycles) at a high scan rate of 1000 mV s−1, outperforming most of the present on-paper MSCs. Furthermore, the heterogeneous MXene/PEDOT:PSS electrodes can interconnect individual MSCs into metal-free on-paper MSC arrays, which can also be simultaneously charged/discharged at 1000 mV s−1, showing scalable capacitive performance. The heterogeneous MXene/PEDOT:PSS stacks are a promising electrode structure for on-paper MSCs to serve as ultrafast miniaturized energy storage components for emerging paper electronics. 

Catalyst passivation through carbon poisoning is a common and costly problem as it reduces the lifetime and performance of the catalyst. Adding oxygen to the feed stream could reduce poisoning but may also affect the activity negatively. We have studied the dehydrogenation, decomposition, and desorption of naphthalene co-adsorbed with oxygen on Ni(111) by combining temperature-programmed desorption (TPD), sum frequency generation spectroscopy (SFG), photoelectron spectroscopy (PES), and density functional theory (DFT). Chemisorbed oxygen reduces the sticking of naphthalene and shifts H2 production and desorption to higher temperatures by blocking active Ni sites. Oxygen increases the production of CO and reduces carbon residues on the surface. Chemisorbed oxygen is readily removed when naphthalene is decomposed. Oxide passivates the surface and reduces the sticking coefficient. But it also increases the production of CO dramatically and reduces the carbon residues. Ni2O3 is more active than NiO.

The growing demands of sustainable, portable, and wearable electronics pose new demands on miniaturized energy storage devices that can be integrated on flexible substrates such as paper. Microsupercapacitors (MSCs), especially MXene-based pseudocapacitive MSCs with fast charging/discharging rate, high power density, and long cycle life, are competitive candidates as power supply for emerging flexible and wearable on-paper electronics. However, few studies have reported MXene-based on-paper MSCs to simultaneously attain ultrahigh-rate (>1000 mV s⁻¹) capability and large areal capacitance >10 mF cm⁻². Herein, ultrafast metal-free on-paper MSCs are fabricated through leveraging the synergistic effect of conductive PEDOT:PSS and capacitive MXene (Ti₂C) to achieve a remarkable areal capacitance of 30 mF cm⁻² and long lifetime (>96% capacitance retention after 10 000 cycles) at an ultrahigh scan rate of 1000 mV s⁻¹, outperforming most of the present on-paper or MXene-containing MSCs. Moreover, the printed on-paper metal-free MSC arrays attain extended working voltage window of up to 6 V and outstanding capacitive performance at an ultrahigh scan rate of 10 V s⁻¹. The on-paper PEDOT:PSS-Ti₂C composite MSCs offer new opportunities as eco-friendly microscale power sources for emerging paper-based portable and wearable electronics.

The instability of molecular electrodes under oxidative/reductive conditions and insufficient understanding of the metal oxide-based systems have slowed down the progress of H2-based fuels. Efficient regeneration of the electrode's performance after prolonged use is another bottleneck of this research. This work represents the first example of a bifunctional and electrochemically regenerable molecular electrode which can be used for the unperturbed production of H2 from water. Pyridyl linkers with flexible arms (-CH2-CH2-) on modified fluorine-doped carbon cloth (FCC) were used to anchor a highly active ruthenium electrocatalyst [RuII(mcbp)(H2O)2] (1) [mcbp2− = 2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine]. The pyridine unit of the linker replaces one of the water molecules of 1, which resulted in RuPFCC (ruthenium electrocatalyst anchored on -CH2-CH2-pyridine modified FCC), a high-performing electrode for oxygen evolution reaction [OER, overpotential of ∼215 mV] as well as hydrogen evolution reaction (HER, overpotential of ∼330 mV) at pH 7. A current density of ∼8 mA cm−2 at 2.06 V (vs. RHE) and ∼−6 mA cm−2 at −0.84 V (vs. RHE) with only 0.04 wt% loading of ruthenium was obtained. OER turnover of >7.4 × 103 at 1.81 V in 48 h and HER turnover of >3.6 × 103 at −0.79 V in 3 h were calculated. The activity of the OER anode after 48 h use could be electrochemically regenerated to ∼98% of its original activity while it serves as a HE cathode (evolving hydrogen) for 8 h. This electrode design can also be used for developing ultra-stable molecular electrodes with exciting electrochemical regeneration features, for other proton-dependent electrochemical processes.

There are several difficulties when experimentally determined reaction mechanisms are applied from model systems to real catalysis. Besides the infamous pressure and material gaps, it is sometimes necessary to consider impurities in the real reactant feedstock that can act as promoters or catalyst poisons and alter the reaction path. In this study, the effect of sulfur on the dehydrogenation of naphthalene on Ni(111) is investigated by using X-ray photoelectron spectroscopy and scanning tunneling microscopy. Sulfur induces a (5 root 3 x 2) surface reconstruction, as previously reported in the literature. The sulfur does not have a strong effect on the dehydrogenation temperature of naphthalene. However, the presence of sulfur leads to a preferred formation of carbidic over graphitic carbon and a strong inhibition of carbon diffusion into the nickel bulk, which is one of the steps of destructive whisker carbon formation described in the catalysis literature.

The low stability of the electrocatalysts at water oxidation (WO) conditions and the use of expensive noble metals have obstructed large-scale H2 production from water. Herein, we report the electrocatalytic WO activity of a cobalt-containing, water-soluble molecular WO electrocatalyst [CoII(mcbp)(OH2)] (1) [mcbp2−=2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine] in homogeneous conditions (overpotential of 510 mV at pH 7 phosphate buffer) and after anchoring it on pyridine-modified fluorine-doped carbon cloth (PFCC). The formation of cobalt phosphate was identified only after 4 h continuous oxygen evolution in homogeneous conditions. Interestingly, a significant enhancement of the stability and WO activity (current density of 5.4 mA/cm2 at 1.75 V) was observed for 1 after anchoring onto PFCC, resulting in a turnover (TO) of >3.6×103 and average TOF of 0.05 s−1 at 1.55 V (pH 7) over 20 h. A total TO of >21×103 over 8 days was calculated. The electrode allowed regeneration of∼ 85 % of the WO activity electrochemically after 36 h of continuous oxygen evolution. 

Carbon monoxide (CO) oxidation is considered an important reaction in heterogeneous industrial catalysis and has been extensively studied. Pd supported on SiO2 aerogel catalysts exhibit good catalytic activity toward this reaction owing to their CO bond activation capability and thermal stability. Pd/SiO2 catalysts were investigated using carbon monoxide (CO) oxidation as a model reaction. The catalyst becomes active, and the conversion increases after the temperature reaches the ignition temperature (T-ig). A normal hysteresis in carbon monoxide (CO) oxidation has been observed, where the catalysts continue to exhibit high catalytic activity (CO conversion remains at 100%) during the extinction even at temperatures lower than T-ig. The catalyst was characterized using BET, TEM, XPS, TGA-DSC, and FTIR. In this work, the influence of pretreatment conditions and stability of the active sites on the catalytic activity and hysteresis is presented. The CO oxidation on the Pd/SiO2 catalyst has been attributed to the dissociative adsorption of molecular oxygen and the activation of the C-O bond, followed by diffusion of adsorbates at T-ig to form CO2. Whereas, the hysteresis has been explained by the enhanced stability of the active site caused by thermal effects, pretreatment conditions, Pd-SiO2 support interaction, and PdO formation and decomposition.

Hypothesis: The self-assembly of amphiphilic molecules onto solid substrates can result both in the formation of monolayers and multilayers. However, on oxidized and non-oxidized copper (Cu), only monolayer formation was reported for phosphonic acids possessing one phosphate head group. Here, the adsorption of octadecylphosphonic acid (ODPA) on Cu substrates through a self-assembly process was investigated with the initial hypothesis of monolayer formation. Experiments: The relative amount of ODPA adsorbed on a Cu substrate was determined by infrared reflection/absorption spectroscopy (IRRAS) and by atomic force microscopy (AFM) investigations before and after ODPA deposition. X-ray photoelectron spectroscopy (XPS) with sputtering was used to characterize the nature of the layers. Findings: The results show that the thickness of the ODPA layer increased with deposition time, and after 1 h a multilayer film with a thickness of some tens of nm was formed. The film was robust and required long-time sonication for removal. The origin of the film robustness was attributed to the release of Cu ions, resulting in the formation of Cu-ODPA complexes with Cu ions in the form of Cu(I). Preadsorbing a monolayer of octadecylthiol (ODT) onto the Cu resulted in no ODPA adsorption, since the release of Cu(I) ions was abolished.