NiFe oxyhydroxide is one of the most promising oxygen evolution reaction (OER) catalysts for renewable hydrogen production, and deciphering the identity and reactivity of the oxygen intermediates on its surface is a key challenge but is critical to understanding the OER mechanism as well as designing water-splitting catalysts with higher efficiencies. Here, we screened and utilized in situ reactive probes that can selectively target specific oxygen intermediates with high rates to investigate the OER intermediates and pathway on NiFe oxyhydroxide. Most importantly, the oxygen atom transfer (OAT) probes (e.g. 4-(Diphenylphosphino) benzoic acid) could efficiently inhibit the OER kinetics by scavenging the OER intermediates, exhibiting lower OER currents, larger Tafel slopes and larger kinetic isotope effect values, while probes with other reactivities demonstrated much smaller effects. Combining the OAT reactivity with electrochemical kinetic and operando Raman spectroscopic techniques, we identified a resting Fe=O intermediate in the Ni-O scaffold and a rate-limiting O-O chemical coupling step between a Fe=O moiety and a vicinal bridging O. DFT calculation further revealed a longer Fe=O bond formed on the surface and a large kinetic energy barrier of the O-O chemical step, corroborating the experimental results. These results point to a new direction of liberating lattice O and expediting O-O coupling for optimizing NiFe-based OER electrocatalyst.
Urea electrolysis is a promising route to utilize urea-rich wastewater as an energy source to produce hydrogen on the cathode or generate electricity through a direct urea fuel cell, which offers great potential for simultaneous water remediation and energy recovery. Here, we report a scalable synthetic strategy to prepare NiCo layer double hydroxide (NiCo LDH) as an efficient catalyst for urea electrooxidation. NiCo LDH with NO3 – intercalant exhibited the best electrocatalytic performance and selectivity toward urea oxidation with a low onset potential, high faradaic efficiency, and high durability. The interlayer spacing in the LDH structure was found to play a pivotal role in the urea oxidation electrocatalysis with higher activity/selectivity under larger spacings. Further analysis of the urea oxidation product could potentially enable selective urine treatment into environmentalally friendly products.
Background The Virtual Electrosurgical Skill Trainer (VEST) is a tool for training surgeons the safe operation of electrosurgery tools in both open and minimally invasive surgery. This training includes a dedicated team-training module that focuses on operating room (OR) fire prevention and response. The module was developed to allow trainees, practicing surgeons, anesthesiologist and nurses to interact with a virtual OR environment, which includes anesthesia apparatus, electrosurgical equipment, a virtual patient, and a fire extinguisher. Wearing a head mounted display, participants must correctly identify the ‘fire triangle’ elements and then successfully contain an OR fire. Within these virtual reality (VR) scenarios, trainees learn to react appropriately to the simulated emergency. A study targeted at establishing the face validity of the virtual OR fire simulator was undertaken at the 2015 Society of American Gastrointestinal and Endoscopic Surgeons (SAGES) conference. Methods Forty-nine subjects with varying experience participated in this Institutional Review Board approved study. The subjects were asked to complete the OR fire training/prevention sequence in the VEST simulator. Subjects were then asked to answer a subjective preference questionnaire consisting of sixteen questions, focused on the usefulness and fidelity of the simulator. Results On a 5-point scale, 12 of 13 questions were rated at a mean of 3 or greater (92%). Five questions were rated above 4 (38%), particularly those focusing on the simulator effectiveness and its usefulness in OR fire safety training. 33 of the 49 participants (67%) chose the virtual OR fire trainer over the traditional training methods such as a textbook or an animal model. Conclusions Training for OR fire emergencies in fully immersive VR environments, such as the VEST trainer, may be the ideal training modality. The face validity of the OR fire training module of the VEST simulator was successfully established on many aspects of the simulation.
Structural regulation of the active centers is often pivotal in controlling the catalytic functions, especially in iron-based oxidation systems. Here, we discovered a significantly altered catalytic oxidation pathway via a simple cation intercalation into a layered iron oxychloride (FeOCl) scaffold. Upon intercalation of FeOCl with potassium iodide (KI), a new stable phase of K +intercalated FeOCl (K-FeOCl) was formed with slided layers, distorted coordination, and formed high-spin Fe(II) species compared to the pristine FeOCl precursor. This structural manipulation steers the catalytic H 2 O 2 activation from a traditional Fenton-like pathway on FeOCl to a nonradical ferryl (Fe(IV)O) pathway. Consequently, the K-FeOCl catalyst can efficiently remove various organic pollutants with almost 2 orders of magnitude faster reaction kinetics than other Fe-based materials via an oxidative coupling or polymerization pathway. A reaction-filtration coupled process based on K-FeOCl was finally demonstrated and could potentially reduce the energy consumption by almost 50%, holding great promise in sustainable pollutant removal technologies.
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