Self-Regenerative Ni-Doped CaTiO3/CaO for Integrated CO2 Capture and Dry Reforming of Methane.

In this work, a new type of multifunctional materials (MFMs) called self-regenerative Ni-doped CaTiO3/CaO is introduced for the integrated CO2 capture and dry reforming of methane (ICCDRM). These materials consist of a catalytically active Ni-doped CaTiO3 and a CO2 sorbent, CaO. The article proposes a concept where the Ni catalyst can be regenerated in situ, which is crucial for ICCDRM. Exsolved Ni nanoparticles are evenly distributed on the surface of CaTiO3 under H2 or CH4, and are re-dispersed back into the CaTiO3 lattice under CO2. The Ni-doped CaTiO3/CaO MFMs show stable CO2 capture capacity and syngas productivity for 30 cycles of ICCDRM. The presence of CaTiO3 between CaO grains prevents CaO/CaCO3 thermal sintering during carbonation and decarbonation. Moreover, the strong interaction of CaTiO3 with exsolved Ni mitigates severe accumulation of coke deposition. This concept can be useful for developing MFMs with improved properties that can advance integrated carbon capture and conversion.

Co-Exsolution of Ni-Based Alloy Catalysts for the Valorization of Carbon Dioxide and Methane.

ConspectusThe reversible coexsolution mechanism of perovskite oxides is emerging as an alternative method for synthesizing alloy catalyst nanoparticles. Co-exsolution is a partial decomposition process where multiple B cations diffuse from the bulk of a solid precursor and nucleate on the surface. The unique properties of exsolved alloy catalysts, including improved dispersion, thermal stability, and compositional malleability, make them particularly useful for converting CO2 into chemical commodities and fuels. However, the coexsolution of alloys is still in development, and fundamental insights into the alloying mechanism, formation of nanoparticles, and defect chemistry are needed.This Account examines the solid-state chemistry of perovskite oxide precursors and reaction parameters that can be altered to control the assembly or exsolution of Ni-based alloys. The characteristics of bulk perovskite oxide precursors heavily influence the exsolved alloy catalyst nanoparticle assembly, growth, and composition. Inherent defects, such as oxygen vacancies and grain boundaries, primarily facilitate the transport of catalytic B-cation dopants from the bulk to the surface. An example of how bulk defects can affect the properties of Ni-based alloy catalysts is demonstrated through the formation of NiFe from La(Fe, Ni)O3. The A/B cation ratio plays a significant role in determining the size and composition of NiFe nanoparticles, which directly impacts their catalytic performance. Using in situ X-ray absorption spectroscopy (in situ XAS), the dynamic behavior of exsolved NiFe nanoparticles can be observed in different reaction environments (oxidation, reduction, and dry reforming of methane) by tracking the oxidation state and local environment of the Ni K-edge and Fe K-edge using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), respectively. Time-resolved experiments with in situ XAS showed that NiFe nanoparticle growth starts at ∼280 °C and transforms from predominantly Ni to NiFe at higher reduction times and temperatures.The challenges of exsolution of higher-order Ni-based alloys, such as 3(NiFeCo), 4(NiCoCuPd), and 5(NiFeCoCuPd) element nanoparticles, to improve the catalyst properties are discussed. The size, concentration, and reducibility of the dopant cation can alter the exsolution kinetics, alloy nanoparticle growth dynamics, and catalyst performance. The size and composition of exsolved Ni-based alloys affect the effectiveness of catalysts in the dry reforming of methane. Large NiFeCo nanoparticles separated from Pd and Cu can lead to catalyst deactivation, but using a complex alloy with smaller NiFeCoPdCu nanoparticles results in a stable performance. The use of in situ XANES reveals how the dry reforming of methane reaction conditions can induce changes in the NiFe with the rapid redissolution of Fe back into the lattice.The dynamicity of the exsolved Ni-based alloy nanoparticles and implications for their regeneration after aging or exposure to waste gas contaminants are discussed. Finally, we summarize the Account and provide promising future directions.

Soft, skin-interfaced microfluidic systems with integrated immunoassays, fluorometric sensors, and impedance measurement capabilities.

Soft microfluidic systems that capture, store, and perform biomarker analysis of microliter volumes of sweat, in situ, as it emerges from the surface of the skin, represent an emerging class of wearable technology with powerful capabilities that complement those of traditional biophysical sensing devices. Recent work establishes applications in the real-time characterization of sweat dynamics and sweat chemistry in the context of sports performance and healthcare diagnostics. This paper presents a collection of advances in biochemical sensors and microfluidic designs that support multimodal operation in the monitoring of physiological signatures directly correlated to physical and mental stresses. These wireless, battery-free, skin-interfaced devices combine lateral flow immunoassays for cortisol, fluorometric assays for glucose and ascorbic acid (vitamin C), and digital tracking of skin galvanic responses. Systematic benchtop evaluations and field studies on human subjects highlight the key features of this platform for the continuous, noninvasive monitoring of biochemical and biophysical correlates of the stress state.

HIGH THROUGHPUT QUANTITATION OF HUMAN NEUTROPHIL RECRUITMENT AND FUNCTIONAL RESPONSES IN AN AIR-BLOOD BARRIER ARRAY.

Dysregulated neutrophil recruitment drives many pulmonary diseases, but most preclinical screening methods are unsuited to evaluate pulmonary neutrophilia, limiting progress towards therapeutics. Namely, high throughput therapeutic screening systems typically exclude critical neutrophilic pathophysiology, including blood-to-lung recruitment, dysfunctional activation, and resulting impacts on the air-blood barrier. To meet the conflicting demands of physiological complexity and high throughput, we developed an assay of 96-well Leukocyte recruitment in an Air-Blood Barrier Array (L-ABBA-96) that enables in vivo -like neutrophil recruitment compatible with downstream phenotyping by automated flow cytometry. We modeled acute respiratory distress syndrome (ARDS) with neutrophil recruitment to 20 ng/mL epithelial-side interleukin 8 (IL-8) and found a dose dependent reduction in recruitment with physiologic doses of baricitinib, a JAK1/2 inhibitor recently FDA-approved for severe COVID-19 ARDS. Additionally, neutrophil recruitment to patient-derived cystic fibrosis sputum supernatant induced disease-mimetic recruitment and activation of healthy donor neutrophils and upregulated endothelial e-selectin. Compared to 24-well assays, the L-ABBA-96 reduces required patient sample volumes by 25 times per well and quadruples throughput per plate. Compared to microfluidic assays, the L-ABBA-96 recruits two orders of magnitude more neutrophils per well, enabling downstream flow cytometry and other standard biochemical assays. This novel pairing of high-throughput in vitro modeling of organ-level lung function with parallel high-throughput leukocyte phenotyping substantially advances opportunities for pathophysiological studies, personalized medicine, and drug testing applications.

A review of wearable biosensors for sweat analysis.

Recent advances in the skin-interfaced wearable sweat sensors allow a personalized daily diagnosis and prognosis of the diseases in a form of a non-invasive, portable, and continuous monitoring system. Especially, the soft microfluidic system provides robust quantitative analysis platforms that integrate sweat sampling, storing, and various sensing capabilities. This review systematically introduces the sweat collecting mechanism using soft microfluidic valves, including calculation of sweat storage and loss. In terms of sweat analysis, colorimetric (e.g. enzymatic, chemical, or their mixed reactions), electrochemical (e.g. voltammetric, potentiometric, amperometric, or conductometric), and multiplex measurements of sweat contents facilitate diagnosis of diseases via analysis of combined multiple data, such as vital signals (e.g. ECG, EMG, EEG, etc.) and information from the skin (e.g. temperature, GSR, etc.). The integration of wireless communication with the microfluidic systems enables point-of-care health monitoring for disease and specific physiological status.

Deactivation of Ni-Al-Based Catalysts for Autothermal Reforming of Diesel Surrogate Fuel in the Presence of an Aromatic Hydrocarbon.

Diesel fuel can produce higher concentrations of H2 and CO gases than other types of hydrocarbon fuels via a reforming reaction for solid oxide fuel cells (SOFCs). However, in addition to sulfur compounds and aromatic hydrocarbons in diesel fuel are a major cause of catalyst deactivation. To elucidate the phenomenon of catalyst deactivation in the presence of an aromatic hydrocarbon, dodecane (C12H26) and hexadecane (C16H34) were blended with an aromatic hydrocarbon such as 1-methylnaphthalene (C11H10) to obtain a diesel surrogate fuel. The experiments were performed for autothermal reforming of the diesel surrogate fuel under conditions of S/C = 1.17, O2/C = 0.24, 750°C and GHSV= 12,000 h-1. Three Ni-Al-based catalysts with 10 wt% (N10A), 30 wt% (N30A) and 50 wt% (N50A) of NiO were prepared via the polymer modified incipient method. Whereas all of the Ni-Al-based catalysts were deactivated with increasing reaction time, the catalysts with greater Ni contents tended to maintain their catalytic performance for a longer time. Correlation between the catalytic performances and Ni content were analyzed by temperature-programmed reduction (TPR), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscope with energy-dispersive X-ray spectroscopy (SEM-EDX), Brunauer-Emmett-Teller(BET) analysis, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Also, we concluded that ethylene (C2H4), which was detected by gas chromatography-mass spectrometry (GC-MS), was the fundamental cause of deactivation of the Ni-Al-based catalysts by accelerating the deposition of wire-type carbon on the catalytic surface.

Soft, skin-interfaced microfluidic systems with integrated enzymatic assays for measuring the concentration of ammonia and ethanol in sweat.

Eccrine sweat is a rich and largely unexplored biofluid that contains a range of important biomarkers, from electrolytes, metabolites, micronutrients and hormones to exogenous agents, each of which can change in concentration with diet, stress level, hydration status and physiologic or metabolic state. Traditionally, clinicians and researchers have used absorbent pads and benchtop analyzers to collect and analyze the biochemical constituents of sweat in controlled, laboratory settings. Recently reported wearable microfluidic and electrochemical sensing devices represent significant advances in this context, with capabilities for rapid, in situ evaluations, in many cases with improved repeatability and accuracy. A limitation is that assays performed in these platforms offer limited control of reaction kinetics and mixing of different reagents and samples. Here, we present a multi-layered microfluidic device platform with designs that eliminate these constraints, to enable integrated enzymatic assays with demonstrations of in situ analysis of the concentrations of ammonia and ethanol in microliter volumes of sweat. Careful characterization of the reaction kinetics and their optimization using statistical techniques yield robust analysis protocols. Human subject studies with sweat initiated by warm-water bathing highlight the operational features of these systems.

Wirelessly controlled, bioresorbable drug delivery device with active valves that exploit electrochemically triggered crevice corrosion.

Implantable drug release platforms that offer wirelessly programmable control over pharmacokinetics have potential in advanced treatment protocols for hormone imbalances, malignant cancers, diabetic conditions, and others. We present a system with this type of functionality in which the constituent materials undergo complete bioresorption to eliminate device load from the patient after completing the final stage of the release process. Here, bioresorbable polyanhydride reservoirs store drugs in defined reservoirs without leakage until wirelessly triggered valve structures open to allow release. These valves operate through an electrochemical mechanism of geometrically accelerated corrosion induced by passage of electrical current from a wireless, bioresorbable power-harvesting unit. Evaluations in cell cultures demonstrate the efficacy of this technology for the treatment of cancerous tissues by release of the drug doxorubicin. Complete in vivo studies of platforms with multiple, independently controlled release events in live-animal models illustrate capabilities for control of blood glucose levels by timed delivery of insulin.