Effect of Polysulfide Speciation on Mg Anode Passivation in Mg-S Batteries.

Mg-S batteries are a promising next-generation system for beyond conventional Li-ion chemistry. The Mg-S architecture pairs a Mg metal anode with an inexpensive, high-capacity S8 cathode. However, S8-based cathodes exhibit the "polysulfide shuttle" effect, wherein soluble partially reduced Sx2- species generated at the cathode diffuse to and react with the anode. While dissolved polysulfides may undergo reactions to form Li+-permeable layers in Li-S systems, the interfaces on Mg anodes are passivating. In this work, we probe the reactivity of various Mg polysulfide solutions at the Mg anode interface. Mg polysulfide solutions are prepared without any chelating agents to closely mimic conditions in a Mg-S cell. The polysulfides are synthesized by reacting Mg metal and S8 in electrolyte, and the speciation is controlled by varying the Mg:S precursor ratio. S-poor precursor ratios produce magnesium polysulfide solutions with a higher proportion of short-chain polysulfides that react at the Mg anode faster than the longer-chain analogues. Anode passivation can be slowed by shifting the polysulfide equilibria toward longer-chain polysulfides through addition of S8.

An Exploration of Sulfur Redox in Lithium Battery Cathodes.

Secondary Li-ion batteries have enabled a world of portable electronics and electrification of personal and commercial transportation. However, the charge storage capacity of conventional intercalation cathodes is reaching the theoretical limit set by the stoichiometry of Li in the fully lithiated structure. Increasing the Li:transition metal ratio and consequently involving structural anions in the charge compensation, a mechanism termed anion redox, is a viable method to improve storage capacities. Although anion redox has recently become the front-runner as a next-generation storage mechanism, the concept has been around for quite some time. In this perspective, we explore the contribution of anions in charge compensation mechanisms ranging from intercalation to conversion and the hybrid mechanisms between. We focus our attention on the redox of S because the voltage required to reach S redox lies within the electrolyte stability window, which removes the convoluting factors caused by the side reactions that plague the oxides. We highlight examples of S redox in cathode materials exhibiting varying degrees of anion involvement with a particular focus on the structural effects. We call attention to those with intermediate anion contribution to redox and the hybrid intercalation- and conversion-type structural mechanism at play that takes advantage of the positives of both mechanistic types to increase storage capacity while maintaining good reversibility. The hybrid mechanisms often invoke the formation of persulfides, and so a survey of binary and ternary materials containing persulfide moieties is presented to provide context for materials that show thermodynamically stable persulfide moieties.

Mg Anode Passivation Caused by the Reaction of Dissolved Sulfur in Mg-S Batteries.

As Li-ion battery optimization approaches theoretical limits, interest has grown in designing next-generation batteries from low-cost earth-abundant materials. Mg-S batteries are promising candidates, exhibiting widespread abundance of elemental precursors and a relatively large theoretical energy density albeit at lower cell voltage. However, Mg-S batteries exhibit poor reversibility, in part due to interactions between dissolved polysulfides and the Mg anode. Herein, we employ electrochemical experiments using Ag2S quasi-reference electrodes to probe the interactions between Mg anodes and dissolved polysulfides. We show that Mg2+ reduction (charging) is impeded in the presence of polysulfides, while Mg metal oxidation (discharging) remains facile. Large reduction overpotentials arise due to the formation of a passivation layer on the anode surface, likely composed primarily of MgS. The passivation layer is removed under oxidative conditions but quickly reforms during reduction. We discover that dissolved S8 influences the rate of MgS formation by shifting the polysulfide disproportionation equilibria. Shorter-chain polysulfides react more readily than longer-chain polysulfides at the Mg electrode, and thus, film formation is mediated by the electrochemical generation of shorter-chain polysulfide species.

Nanoscale semiconductor/catalyst interfaces in photoelectrochemistry.

Semiconductor structures (for example, films, wires, particles) used in photoelectrochemical devices are often decorated with nanoparticles that catalyse fuel-forming reactions, including water oxidation, hydrogen evolution or carbon-dioxide reduction. For high performance, the catalyst nanoparticles must form charge-carrier-selective contacts with the underlying light-absorbing semiconductor, facilitating either hole or electron transfer while inhibiting collection of the opposite carrier. Despite the key role played by such selective contacts in photoelectrochemical energy conversion and storage, the underlying nanoscale interfaces are poorly understood because direct measurement of their properties is challenging, especially under operating conditions. Using an n-Si/Ni photoanode model system and potential-sensing atomic force microscopy, we measure interfacial electron-transfer processes and map the photovoltage generated during photoelectrochemical oxygen evolution at nanoscopic semiconductor/catalyst interfaces. We discover interfaces where the selectivity of low-Schottky-barrier n-Si/Ni contacts for holes is enhanced via a nanoscale size-dependent pinch-off effect produced when surrounding high-barrier regions develop during device operation. These results thus demonstrate (1) the ability to make nanoscale operando measurements of contact properties under practical photoelectrochemical conditions and (2) a design principle to control the flow of electrons and holes across semiconductor/catalyst junctions that is broadly relevant to different photoelectrochemical devices.

Metal Oxide/(oxy)hydroxide Overlayers as Hole Collectors and Oxygen-Evolution Catalysts on Water-Splitting Photoanodes.

Solar water splitting provides a mechanism to convert and store solar energy in the form of stable chemical bonds. Water-splitting systems often include semiconductor photoanodes, such as n-Fe2O3 and n-BiVO4, which use photogenerated holes to oxidize water. These photoanodes often exhibit improved performance when coated with metal-oxide/(oxy)hydroxide overlayers that are catalytic for the water-oxidation reaction. The mechanism for this improvement, however, remains a controversial topic. This is, in part, due to a lack of experimental techniques that are able to directly track the flow of photogenerated holes in such multicomponent systems. In this Perspective, we illustrate how this issue can be addressed by using a second working electrode to make direct current/voltage measurements on the catalytic overlayer during operation in a photoelectrochemical cell. We discuss examples where the second working electrode is a thin metallic film deposited on the catalyst layer, as well as where it is the tip of a conducting atomic-force-microscopy probe. In applying these techniques to multiple semiconductors (Fe2O3, BiVO4, Si) paired with various metal-(oxy)hydroxide overlayers (e.g., Ni(Fe)O xH y and CoO xH y), we found in all cases investigated that the overlayers collect photogenerated holes from the semiconductor, charging to potentials sufficient to drive water oxidation. The overlayers studied thus form charge-separating heterojunctions with the semiconductor as well as serve as water-oxidation catalysts.

Direct in Situ Measurement of Charge Transfer Processes During Photoelectrochemical Water Oxidation on Catalyzed Hematite.

Electrocatalysts improve the efficiency of light-absorbing semiconductor photoanodes driving the oxygen evolution reaction, but the precise function(s) of the electrocatalysts remains unclear. We directly measure, for the first time, the interface carrier transport properties of a prototypical visible-light-absorbing semiconductor, α-Fe2O3, in contact with one of the fastest known water oxidation catalysts, Ni0.8Fe0.2O x , by directly measuring/controlling the current and/or voltage at the Ni0.8Fe0.2O x catalyst layer using a second working electrode. The measurements demonstrate that the majority of photogenerated holes in α-Fe2O3 directly transfer to the catalyst film over a wide range of conditions and that the Ni0.8Fe0.2O x is oxidized by photoholes to an operating potential sufficient to drive water oxidation at rates that match the photocurrent generated by the α-Fe2O3. The Ni0.8Fe0.2O x therefore acts as both a hole-collecting contact and a catalyst for the photoelectrochemical water oxidation process. Separate measurements show that the illuminated junction photovoltage across the α-Fe2O3|Ni0.8Fe0.2O x interface is significantly decreased by the oxidation of Ni2+ to Ni3+ and the associated increase in the Ni0.8Fe0.2O x electrical conductivity. In sum, the results illustrate the underlying operative charge-transfer and photovoltage generation mechanisms of catalyzed photoelectrodes, thus guiding their continued improvement.

Semiconductor-Electrocatalyst Interfaces: Theory, Experiment, and Applications in Photoelectrochemical Water Splitting.

Light-absorbing semiconductor electrodes coated with electrocatalysts are key components of photoelectrochemical energy conversion and storage systems. Efforts to optimize these systems have been slowed by an inadequate understanding of the semiconductor-electrocatalyst (sem|cat) interface. The sem|cat interface is important because it separates and collects photoexcited charge carriers from the semiconductor. The photovoltage generated by the interface drives "uphill" photochemical reactions, such as water splitting to form hydrogen fuel. Here we describe efforts to understand the microscopic processes and materials parameters governing interfacial electron transfer between light-absorbing semiconductors, electrocatalysts, and solution. We highlight the properties of transition-metal oxyhydroxide electrocatalysts, such as Ni(Fe)OOH, because they are the fastest oxygen-evolution catalysts known in alkaline media and are (typically) permeable to electrolyte. We describe the physics that govern the charge-transfer kinetics for different interface types, and show how numerical simulations can explain the response of composite systems. Emphasis is placed on "limiting" behavior. Electrocatalysts that are permeable to electrolyte form "adaptive" junctions where the interface energetics change during operation as charge accumulates in the catalyst, but is screened locally by electrolyte ions. Electrocatalysts that are dense, and thus impermeable to electrolyte, form buried junctions where the interface physics are unchanged during operation. Experiments to directly measure the interface behavior and test the theory/simulations are challenging because conventional photoelectrochemical techniques do not measure the electrocatalyst potential during operation. We developed dual-working-electrode (DWE) photoelectrochemistry to address this limitation. A second electrode is attached to the catalyst layer to sense or control current/voltage independent from that of the semiconductor back ohmic contact. Consistent with simulations, electrolyte-permeable, redox-active catalysts such as Ni(Fe)OOH form "adaptive" junctions where the effective barrier height for electron exchange depends on the potential of the catalyst. This is in contrast to sem|cat interfaces with dense electrolyte-impermeable catalysts, such as nanocrystalline IrOx, that behave like solid-state buried (Schottky-like) junctions. These results elucidate a design principle for catalyzed photoelectrodes. The buried heterojunctions formed by dense catalysts are often limited by Fermi-level pinning and low photovoltages. Catalysts deposited by "soft" methods, such as electrodeposition, form adaptive junctions that tend to provide larger photovoltages and efficiencies. We also preview efforts to improve theory/simulations to account for the presence of surface states and discuss the prospect of carrier-selective catalyst contacts.

The measurement of magnesium: a possible key to struvite production and process control.

Struvite, a crystalline structure comprised of ions of magnesium (Mg2+), ammonium (NH4-N) and phosphate (PO4-P), is commonly encountered in wastewater treatmentplants (WWTPs) through struvite encrustation. The gradual growth of this crystal can lead to h igh maintenance costs, due to downtime and replacement parts. Several struvite recovery unit processes have been developed in an effort to reduce this problem, through the preferential removal of the constituent ions (Mg2+, NH4-N, and PO4-P) upstream of problem areas (e.g. anaerobic digester supernatants). One of the key elements of process control for these systems is accurately determining the constituent concentrations. Although a wide variety of measurement techniques exist for both NH4-N and PO4-P, the presence of PO4-P interferes with the measurement of Mg2+. Ion selective electrodes (ISEs) were tested on wastewater samples to determine Mg2+ concentrations. It was found that the two ISE tested produced unreliable results, as they both proved non-specific t o Mg2+. A modification, using polyaluminum chloride (PAC), was developed to remove the interference of phosphates from the colorimetric technique. It was found to produce reliable results within 10% of those results predicted by atomic absorption. The resulting technique averaged about 10 minutes per sample and could be conducted inexpensively at a laboratory facility at WWTPs.

The clinical and metabolic responses to early surgical treatment for hyperthyroid Graves' disease: a comparison of three pre-operative treatment regimens.

We have compared the clinical and metabolic responses of three groups of patients undergoing subtotal thyroidectomy for hyperthyroid Graves' disease. These patients were prepared for surgery with propranolol alone, propranolol plus potassium iodide or the long acting beta-adrenoceptor antagonist nadolol plus potassium iodide. Pre-treatment with potassium iodide reduced serum T4 to normal or subnormal in all patients. Patients in the propranolol group had significantly higher pulse rates and temperatures after operation and one patient developed an exacerbation of the hypermetabolic state. The perioperative rise in serum cortisol and blood glucose was delayed in patients in the propranolol group and this was also noted in one severely hyperthyroid patient on propranolol + potassium iodide. Nadolol was administered once daily as compared to multiple daily doses with propranolol. Despite this, plasma nadolol levels were consistently higher throughout the perioperative period while propranolol levels in patients on both propranolol alone and propranolol + potassium iodide were highly variable and sometimes undetectable. We conclude that, in the rapid preparation of patients with hyperthyroid Graves' disease for surgery, the combination of nadolol + potassium iodide has significant advantages over the other two regimens.

Patient monitoring in the operating theatre. A comparison of practice between 1976 and 1983.

The vital importance of patient monitoring during anaesthesia is well recognised. There is little information available, however, on the actual practice of instrumental monitoring in the operating theatre. This study examined present-day practice and compared it with that of 1976. The main findings were an increase in frequency of electrocardiographic monitoring, especially for non-major surgery, and a smaller increase in blood pressure recording. Monitoring of other variables remained essentially unchanged. Possible reasons for this are given and suggestions made for improvements.

Beta-adrenoceptor blockade and anaesthesia for thyroidectomy.

The administration of beta-adrenoceptor blocking drugs in the pre-operative preparation and operative management of thyrotoxic patients undergoing subtotal thyroidectomy is reviewed. Particular reference is made to some of the recent advances and it is emphasised that there has been a considerable reduction in the incidence of problems following judicious use of these drugs. The choice of anaesthetic technique employed for thyroidectomy is less important than the degree of control of thyrotoxicosis by the beta-adrenoceptor blocking drug. Propranolol has proved safe and effective for the majority of patients. The longer acting agent nadolol is easier to administer, particularly in the peri-operative period. Patients are rendered less thyrotoxic and safety thereby enhanced by adding potassium iodide for 10 days preoperatively. The combination of nadolol and potassium iodide offers real advantages in the preparation of the thyrotoxic patient for surgery.

Nadolol and potassium iodide in combination in the surgical treatment of thyrotoxicosis.

With the two aims of rapidly reducing circulating thyroid hormone levels and controlling the symptoms of thyrotoxicosis, we have prepared 17 thyrotoxic patients for subtotal thyroidectomy, using a combination of potassium iodide administered for 10 days and the long acting beta-adrenoceptor antagonist nadolol. All 17 patients had normal serum thyroxine levels after 10 days of such treatment although 10 still showed elevation of serum tri-iodothyronine and considerable elevation in the most severely toxic patient. All patients were, however, clinically euthyroid preoperatively. Nadolol was administered once daily, hence avoiding the problems of drug administration in the immediate postoperative period, and plasma nadolol concentrations were high throughout the perioperative period. Serum thyroxine and tri-iodothyronine levels were significantly lower and reverse tri-iodothyronine levels higher 24 h postoperatively than before operation. All patients remained stable throughout the perioperative period. We conclude that this regimen has a number of advantages in the preparation of patients for thyroidectomy, in reducing the degree of thyrotoxicosis, in convenience of drug administration and in ensuring adequate circulating concentrations of beta-adrenoceptor antagonist whilst still retaining a relatively short preoperative phase of drug treatment.

Propranolol in the surgical treatment of hyperthyroidism, including severely thyrotoxic patients.

The perioperative course of 44 hyperthyroid patients prepared for surgery with propranolol alone, including 11 with severe thyrotoxicosis was compared to that of 20 euthyroid patients prepared for surgery with carbimazole. Conventional propranolol at a dosage of 160 mg/day was frequently insufficient to produce a high degree of beta-adrenergic blockade, particularly in severely thyrotoxic patients. A greater than 25 per cent reduction in sitting pulse rate was associated with a high degree of beta-blockade. The clinical course of patients with mild or moderate thyrotoxicosis was similar to that of the patients prepared with carbimazole. In contrast, the course of severely thyrotoxic patients was complicated and, in addition to a higher preoperative propranolol dosage, these patients commonly required supplemental propranolol after operation. Although thyroid crisis did not occur in any patient, we cannot recommend the use of propranolol alone for the severely thyrotoxic patient.

Altered endocrine response to partial thyroidectomy in propranolol-prepared hyperthyroid patients.

The endocrine response to partial thyroidectomy in a group of twenty hyperthyroid patients prepared with propranolol alone was compared to that of a matched control group of ten euthyroid patients. In propranolol-prepared patients the glucose response to surgery was reduced (P less than 0.05) for up to 4 h post-operatively and biochemical hypoglycaemia was noted in one patient. Both thyroxine and triiodothyronine (T3) fell significantly, associated with a marked rise in reverse T3. Growth hormone levels were higher (P less than 0.05) both pre- and post-operatively in propranolol-prepared patients, whereas prolactin levels, although similar pre-operatively, were lower (P less than 0.05) in these patients post-operatively. Cortisol and ACTH levels were lower (P less than 0.05) both before and following thyroidectomy in propranolol-prepared patients. These results suggest that the endocrine response to surgical stress is markedly altered in propranolol-prepared hyperthyroid patients.

Reports by anaesthetists to procurators-fiscal: analysis of "anaesthetic deaths" over 10 years in four Scottish teaching hospitals.

Review of 489 "anaesthetic deaths" reported to procurators-fiscal over 10 years disclosed only 30 that were thought to justify such reporting. Most of the remainder occurred in patients so desperately ill at the time of operation that death was expected. Postmortem examinations ordered by the Crown authorities in nearly all cases were probably largely unrewarding and mostly unnecessary. The results suggest that the present regulation on reporting should be revised to focus more attention on the few deaths that occur in patients who have no apparent contraindication to anaesthesia or operation.

Patient monitoring in the operating theatre.

Anaesthetised patients are monitored to ensure their safety. Simple clinical observations must not be replaced by electronic instruments--these provide an extension of the clinical senses. The choice of parameters for monitoring is discussed. The design of the Ninewells main operating theatre suite is described. An 8-channel bourne in the base of the theatre table conveys patient signals to a 4-channel recorder in a monitoring laboratory. Outputs are displayed on a wall mounted display in theatre. Two-way speech intercommunication exists with monitoring technician and students.