CO2 doping of organic interlayers for perovskite solar cells.

In perovskite solar cells, doped organic semiconductors are often used as charge-extraction interlayers situated between the photoactive layer and the electrodes. The π-conjugated small molecule 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9-spirobifluorene (spiro-OMeTAD) is the most frequently used semiconductor in the hole-conducting layer1-6, and its electrical properties considerably affect the charge collection efficiencies of the solar cell7. To enhance the electrical conductivity of spiro-OMeTAD, lithium bis(trifluoromethane)sulfonimide (LiTFSI) is typically used in a doping process, which is conventionally initiated by exposing spiro-OMeTAD:LiTFSI blend films to air and light for several hours. This process, in which oxygen acts as the p-type dopant8-11, is time-intensive and largely depends on ambient conditions, and thus hinders the commercialization of perovskite solar cells. Here we report a fast and reproducible doping method that involves bubbling a spiro-OMeTAD:LiTFSI solution with CO2 under ultraviolet light. CO2 obtains electrons from photoexcited spiro-OMeTAD, rapidly promoting its p-type doping and resulting in the precipitation of carbonates. The CO2-treated interlayer exhibits approximately 100 times higher conductivity than a pristine film while realizing stable, high-efficiency perovskite solar cells without any post-treatments. We also show that this method can be used to dope π-conjugated polymers.

High-throughput, combinatorial synthesis of multimetallic nanoclusters.

Multimetallic nanoclusters (MMNCs) offer unique and tailorable surface chemistries that hold great potential for numerous catalytic applications. The efficient exploration of this vast chemical space necessitates an accelerated discovery pipeline that supersedes traditional "trial-and-error" experimentation while guaranteeing uniform microstructures despite compositional complexity. Herein, we report the high-throughput synthesis of an extensive series of ultrafine and homogeneous alloy MMNCs, achieved by 1) a flexible compositional design by formulation in the precursor solution phase and 2) the ultrafast synthesis of alloy MMNCs using thermal shock heating (i.e., ∼1,650 K, ∼500 ms). This approach is remarkably facile and easily accessible compared to conventional vapor-phase deposition, and the particle size and structural uniformity enable comparative studies across compositionally different MMNCs. Rapid electrochemical screening is demonstrated by using a scanning droplet cell, enabling us to discover two promising electrocatalysts, which we subsequently validated using a rotating disk setup. This demonstrated high-throughput material discovery pipeline presents a paradigm for facile and accelerated exploration of MMNCs for a broad range of applications.

In Operando Visualization and Dynamic Manipulation of Electrochemical Processes at the Electrode-Solution Interface.

Revealing the dynamic processes at the electrode-solution interface is imperative for understanding electrochemical phenomena. Most techniques have been developed to sense the electrode surface changes at the nanoscale, but provide limited information on potential-induced interfacial ion redistribution at the mesoscale. Herein, we present an in operando visualization method utilizing a microfabricated electrochemical cell combined with a laser scanning confocal microscope to observe high-resolution and fast-response interfacial processes. We report potential-induced formation and transformation of the Nernst diffusion layer, demonstrating that pulsed voltage dynamically perturbs the interface and promotes ion diffusion. This provides an additional insight into developing a dynamic manipulation method to control the electrochemical process. Our novel visualization method can easily be applied to monitor different ionic behaviors in electrochemical reactions at the mesoscale.

Electrochemical-Osmotic Process for Simultaneous Recovery of Electric Energy, Water, and Metals from Wastewater.

A highly-efficient, autonomous electrochemical-osmotic system (EOS) is developed for simultaneous recovery of electric energy, water, and metals from wastewater. We demonstrate that the system can generate a maximum electric power density of 10.5 W m-2 using a spontaneous Fe/Cu2+ galvanic cell, while simultaneously achieving copper recovery from wastewater. With an osmotic pressure difference generated by the deployed electrochemical reactions, water is osmotically extracted from the feed solution with the EOS at a water flux of 5.1 L m-2 h-1. A scaled-up EOS realizes a power density of 105.8 W per m-3 of treated water to light an LED over 24 h while also enhancing water extraction and metal recovery. The modularized EOS obtains ultrahigh (>97.5%) Faradaic efficiencies under variable operating conditions, showing excellent system stability. The EOS is also versatile: it can recover Au, Ag, and Hg from wastewaters with simultaneous electricity and water coproduction. Our study demonstrates a promising pathway for realizing multiresource recycling from wastewater by coupling electrochemical and osmosis-driven processes.

A Promising Carbon/g-C3 N4 Composite Negative Electrode for a Long-Life Sodium-Ion Battery.

2D graphitic carbon nitride (g-C3 N4 ) nanosheets are a promising negative electrode candidate for sodium-ion batteries (NIBs) owing to its easy scalability, low cost, chemical stability, and potentially high rate capability. However, intrinsic g-C3 N4 exhibits poor electronic conductivity, low reversible Na-storage capacity, and insufficient cyclability. DFT calculations suggest that this could be due to a large Na+ ion diffusion barrier in the innate g-C3 N4 nanosheet. A facile one-pot heating of a mixture of low-cost urea and asphalt is strategically applied to yield stacked multilayer C/g-C3 N4 composites with improved Na-storage capacity (about 2 times higher than that of g-C3 N4 , up to 254 mAh g-1 ), rate capability, and cyclability. A C/g-C3 N4 sodium-ion full cell (in which sodium rhodizonate dibasic is used as the positive electrode) demonstrates high Coulombic efficiency (ca. 99.8 %) and a negligible capacity fading over 14 000 cycles at 1 A g-1 .

Charge Transfer from Carbon Nanotubes to Silicon in Flexible Carbon Nanotube/Silicon Solar Cells.

Mechanical fragility and insufficient light absorption are two major challenges for thin flexible crystalline Si-based solar cells. Flexible hybrid single-walled carbon nanotube (SWNT)/Si solar cells are demonstrated by applying scalable room-temperature processes for the fabrication of solar-cell components (e.g., preparation of SWNT thin films and SWNT/Si p-n junctions). The flexible SWNT/Si solar cells present an intrinsic efficiency ≈7.5% without any additional light-trapping structures. By using these solar cells as model systems, the charge transport mechanisms at the SWNT/Si interface are investigated using femtosecond transient absorption. Although primary photon absorption occurs in Si, transient absorption measurements show that SWNTs also generate and inject excited charge carriers to Si. Such effects can be tuned by controlling the thickness of the SWNTs. Findings from this study could open a new pathway for designing and improving the efficiency of photocarrier generation and absorption for high-performance ultrathin hybrid SWNT/Si solar cells.

A New Design Strategy for Observing Lithium Oxide Growth-Evolution Interactions Using Geometric Catalyst Positioning.

Understanding the catalyzed formation and evolution of lithium-oxide products in Li-O2 batteries is central to the development of next-generation energy storage technology. Catalytic sites, while effective in lowering reaction barriers, often become deactivated when placed on the surface of an oxygen electrode due to passivation by solid products. Here we investigate a mechanism for alleviating catalyst deactivation by dispersing Pd catalytic sites away from the oxygen electrode surface in a well-structured anodic aluminum oxide (AAO) porous membrane interlayer. We observe the cross-sectional product growth and evolution in Li-O2 cells by characterizing products that grow from the electrode surface. Morphological and structural details of the products in both catalyzed and uncatalyzed cells are investigated independently from the influence of the oxygen electrode. We find that the geometric decoration of catalysts far from the conductive electrode surface significantly improves the reaction reversibility by chemically facilitating the oxidation reaction through local coordination with PdO surfaces. The influence of the catalyst position on product composition is further verified by ex situ X-ray photoelectron spectroscopy and Raman spectroscopy in addition to morphological studies.

A mesoporous catalytic membrane architecture for lithium-oxygen battery systems.

Controlling the mesoscale geometric configuration of catalysts on the oxygen electrode is an effective strategy to achieve high reversibility and efficiency in Li-O2 batteries. Here we introduce a new Li-O2 cell architecture that employs a catalytic polymer-based membrane between the oxygen electrode and the separator. The catalytic membrane was prepared by immobilization of Pd nanoparticles on a polyacrylonitrile (PAN) nanofiber membrane and is adjacent to a carbon nanotube electrode loaded with Ru nanoparticles. During oxide product formation, the insulating PAN polymer scaffold restricts direct electron transfer to the Pd catalyst particles and prevents the direct blockage of Pd catalytic sites. The modified Li-O2 battery with a catalytic membrane showed a stable cyclability for 60 cycles with a capacity of 1000 mAh/g and a reduced degree of polarization (∼ 0.3 V) compared to cells without a catalytic membrane. We demonstrate the effects of a catalytic membrane on the reaction characteristics associated with morphological and structural features of the discharge products via detailed ex situ characterization.

Role of HF in oxygen removal from carbon nanotubes: implications for high performance carbon electronics.

Oxygen removal from SWNTs is crucial for many carbon electronic devices. This work shows that HF treatment followed by current stimulation is a very effective method for oxygen removal. Using a procedure involving HF treatment, current stimulation and spin-casting AgNWs onto a SWNT thin film, record high efficiency SWNT/p-Si solar cells have been developed.

Controlled doping of carbon nanotubes with metallocenes for application in hybrid carbon nanotube/Si solar cells.

There is considerable interest in the controlled p-type and n-type doping of carbon nanotubes (CNT) for use in a range of important electronics applications, including the development of hybrid CNT/silicon (Si) photovoltaic devices. Here, we demonstrate that easy to handle metallocenes and related complexes can be used to both p-type and n-type dope single-walled carbon nanotube (SWNT) thin films, using a simple spin coating process. We report n-SWNT/p-Si photovoltaic devices that are >450 times more efficient than the best solar cells of this type currently reported and show that the performance of both our n-SWNT/p-Si and p-SWNT/n-Si devices is related to the doping level of the SWNT. Furthermore, we establish that the electronic structure of the metallocene or related molecule can be correlated to the doping level of the SWNT, which may provide the foundation for controlled doping of SWNT thin films in the future.

Toward tailored functional design of multi-walled carbon nanotubes (MWNTs): electrochemical and antimicrobial activity enhancement via oxidation and selective reduction.

Multiwalled carbon nanotubes (MWNTs) are utilized in a number of sectors as a result of their favorable electronic properties. In addition, MWNT antimicrobial properties can be exploited or considered a potential liability depending on their intended application and handling. The ability to tailor electrochemical and antimicrobial properties using economical and conventional treatment processes introduces the potential to significantly enhance product performance. Oxygen functional groups are known to influence several MWNT properties, including redox activity. Here, MWNTs were functionalized with oxygen groups using standard acid treatments followed by selective reduction via annealing. Chemical derivatization coupled to X-ray photoelectron spectroscopy was utilized to quantify specific surface oxygen group concentration after variable treatment conditions, which were then correlated to observed trends in electrochemical and antimicrobial activities. These activities were evaluated as the potential for MWNTs to participate in the oxygen reduction reaction and to have the ability to promote the oxidation of glutathione. The compiled results strongly suggest that the reduction of surface carboxyl groups and the redox activity of carbonyl groups promote enhanced MWNT reactivity and elucidate the opportunity to design functional MWNTs for enhanced performance in their intended electrochemical or antimicrobial application.

Catalyst and electrolyte synergy in Li-O2 batteries.

Understanding the interactions between catalyst and electrolyte in Li-O2 systems is crucial to improving capacities, efficiencies, and cycle life. In this study, supported noble metal catalysts Pt/C, Pd/C, and Au/C were paired with popular Li-O2 electrolyte solvents dimethoxyethane (DME), tetraglyme (TEGDME), and dimethyl sulfoxide (DMSO). The effects of these combinations on stability, kinetics, and activity were assessed. We show evidence of a synergistic effect between Pt and Pd catalysts and a DMSO-based electrolyte which enhances the kinetics of oxygen reduction and evolution reactions. DME and TEGDME are more prone to decomposition and less kinetically favorable for oxygen reduction and evolution than DMSO. While the order of oxygen reduction onset potentials with each catalyst was found to be consistent across electrolyte (Pd > Pt > Au), larger overpotentials with DME and TEGDME, and negative shifts in onset after only five cycles favor the stability of a DMSO electrolyte. Full cell cycling experiments confirm that catalyst-DMSO combinations produce up to 9 times higher discharge capacities than the same with TEGDME after 20 cycles (∼707.4 vs. 78.8 mA h g(-1) with Pd/C). Ex situ EDS and in situ EIS analyses of resistive species in the cathode suggest that improvements in capacity with DMSO are due to a combination of greater electrolyte conductivity and catalyst synergies. Our findings demonstrate that co-selection of catalyst and electrolyte is necessary to exploit chemical synergies and improve the performance of Li-O2 cells.

Record high efficiency single-walled carbon nanotube/silicon p-n junction solar cells.

Carrier transport characteristics in high-efficiency single-walled carbon nanotubes (SWNTs)/silicon (Si) hybrid solar cells are presented. The solar cells were fabricated by depositing intrinsic p-type SWNT thin-films on n-type Si wafers without involving any high-temperature process for p-n junction formation. The optimized cells showed a device ideality factor close to unity and a record-high power-conversion-efficiency of >11%. By investigating the dark forward current density characteristics with varying temperature, we have identified that the temperature-dependent current rectification originates from the thermally activated band-to-band transition of carriers in Si, and the role of the SWNT thin films is to establish a built-in potential for carrier separation/collection. We have also established that the dominant carrier transport mechanism is diffusion, with minimal interface recombination. This is further supported by the observation of a long minority carrier lifetime of ~34 µs, determined by the transient recovery method. This study suggests that these hybrid solar cells operate in the same manner as single crystalline p-n homojunction Si solar cells.

LED-based characterization of solar cells for underwater applications.

Improved solar energy harvesting in aquatic environments would allow for superior environmental monitoring. However, developing underwater solar cells is challenging as evaluation typically requires deployment in the field or in large water tanks that can simulate aquatic light conditions. Here, we present a protocol to test underwater solar cells using a light-emitting diode (LED)-based characterization technique usable in a typical laboratory setting. We describe steps for installing and running Python code, matching LEDs to irradiance, characterizing underwater solar cells, and calculating underwater solar cell efficiency. For complete details on the use and execution of this protocol, please refer to Röhr et al.1.

Hierarchical Transparent Back Contacts for Bifacial CdTe PV.

A hierarchical transparent back contact leveraging an AlGaOx passivating layer, Ti3C2Tx MXene with a high work function, and a transparent cracked film lithography (CFL) templated nanogrid is demonstrated on copper-free cadmium telluride (CdTe) devices. AlGaOx improves device open-circuit voltage but reduces the fill factor when using a CFL-templated metal contact. Including a Ti3C2Tx interlayer improves the fill factor, lowers detrimental Schottky barriers, and enables metallization with CFL by providing transverse conduction into the nanogrid. The bifacial performance of an AlGaOx/Ti3C2Tx/CFL gold contact is evaluated, reaching 19.5% frontside efficiency and 2.8% backside efficiency under 1-sun illumination for a copper-free, group-V doped CdTe device. Under dual illumination, device power generation reached 200 W/m2 with 0.1 sun backside illumination.

Realizing comparable oxidative and cytotoxic potential of single- and multiwalled carbon nanotubes through annealing.

The potential applications as well as the environmental and human health implications of carbon nanomaterials are well represented in the literature. There has been a recent focus on how specific physicochemical properties influence carbon nanotube (CNT) function as well as cytotoxicity. The ultimate goal is a better understanding of the causal relationship between fundamental physiochemical properties and cytotoxic mechanism in order to both advance functional design and to minimize unintended consequences of CNTs. This study provides characterization data on a series of multiwalled carbon nanotubes (MWNTs) that underwent acid treatment followed by annealing at increasing temperatures, ranging from 400 to 900 °C. These results show that MWNTs can be imparted with the same toxicity as single-walled carbon nanotubes (SWNTs) by acid treatment and annealing. Further, we were able to correlate this toxicity to the chemical reactivity of the MWNT suggesting that it is a chemical rather than physical hazard. This informs the design of MWNT to be less hazardous or enables their implementation in antimicrobial applications. Given the reduced cost and ready dispersivity of MWNTs as compared to SWNTs, there is a significant opportunity to pursue the use of MWNTs in novel applications previously thought reserved for SWNTs.

Blending genetics and sociocultural historical inquiry: ethics, culture, and human subjects protection in international cross cultural research.

In this paper, we examine the implementation and difficulties when conducting genetics research in a rural, traditional West African culture within the frame of the United States' grounded research ethics. Research challenges are highlighted by Western researchers following U.S. Institutional Review Board (IRB) guidelines and practices in a non-Western country. IRB concepts are culture bound in Western ideals that may not have synchronicity and compatibility with non-Western cultures. Differences in sociocultural norms, traditions, language, and geography were influencing factors that can affect application of IRB principles. Suggestions for change are offered, which will potentially aid researchers considering application of IRB requirements when conducting research in non-Westernized, non-industrialized countries.

Towards High-Efficiency Photon Trapping in Thin-Film Perovskite Solar Cells Using Etched Fractal Metadevices.

Reflective loss is one of the main factors contributing to power conversion efficiency limitation in thin-film perovskite solar cells. This issue has been tackled through several approaches, such as anti-reflective coatings, surface texturing, or superficial light-trapping metastructures. We report detailed simulation-based investigations on the photon trapping capabilities of a standard Methylammonium Lead Iodide (MAPbI3) solar cell, with its top layer conveniently designed as a fractal metadevice, to reach a reflection value R<0.1 in the visible domain. Our results show that, under certain architecture configurations, reflection values below 0.1 are obtained throughout the visible domain. This represents a net improvement when compared to the 0.25 reflection yielded by a reference MAPbI3 having a plane surface, under identical simulation conditions. We also present the minimum architectural requirements of the metadevice by comparing it to simpler structures of the same family and performing a comparative study. Furthermore, the designed metadevice presents low power dissipation and exhibits approximately similar behavior regardless of the incident polarization angle. As a result, the proposed system is a viable candidate for being a standard requirement in obtaining high-efficiency perovskite solar cells.

Effects of parity on blood pressure among West African Dogon women.

OBJECTIVE: This study examined the effect of parity on blood pressure (BP) readings and BMI among rural West African Dogon women. DESIGN: Correlational research design. SETTING: Sangha, West Africa PARTICIPANTS: 133 West African Dogon Women METHODS: Demographic survey including age, number of children, history of hypertension, and village affiliation. BP readings were taken in accordance with JNC-7 guidelines. BMI was calculated from height and weight. RESULTS: Women with BP readings diagnostic of hypertension were typically older (M = 55.72 years) than those who were normotensive (M = 42.40). However, BMI, on average, was within normal range for both groups (22.81 and 22.15, respectively). A statistically significant difference was found between number of children and systolic BP (SBP), P = .015, with those having 5 or more children with higher SBP than those with one to three children. A statistically significant difference, P = .001, was found between hypertension and normotensive diagnostic groups. CONCLUSIONS: This study shows that increased parity of five or more children may contribute to West African Dogon women's risk factors for hypertension in terms of increased SBP. Because BMI was within normal range for both groups of women, it was not shown to be an independent risk factor for hypertension in this sample. Further studies, with larger samples followed throughout their childbearing years (before, during, and after each pregnancy), are needed before more definitive conclusions can be made regarding the effects of parity on BMI and BP among rural West African Dogon women.