Watching You: Systematic Federal Surveillance of Ordinary Americans

To combat terrorism, Attorney General John Ashcroft has asked Congress to "enhance" the government's ability to conduct domestic surveillance of citizens. The Justice Department's legislative proposals would give federal law enforcement agents new access to personal information contained in business and school records. Before acting on those legislative proposals, lawmakers should pause to consider the extent to which the lives of ordinary Americans already are monitored by the federal government. Over the years, the federal government has instituted a variety of data collection programs that compel the production, retention, and dissemination of personal information about every American citizen. Linked through an individual's Social Security number, these labor, medical, education and financial databases now empower the federal government to obtain a detailed portrait of any person: the checks he writes, the types of causes he supports, and what he says "privately" to his doctor. Despite widespread public concern about preserving privacy, these data collection systems have been enacted in the name of "reducing fraud" and "promoting efficiency" in various government programs. Having exposed most areas of American life to ongoing government scrutiny and recording, Congress is now poised to expand and universalize federal tracking of citizen life. The inevitable consequence of such constant surveillance, however, is metastasizing government control over society. If that happens, our government will have perverted its most fundamental mission and destroyed the privacy and liberty that it was supposed to protect

From Claiming Credit to Avoiding Blame: The Evolution of Congressional Strategy for Asbestos Management

This paper develops a theory synthesizing credit-claiming and blame-avoidance explanations of congressional behavior and evaluates it against asbestos policy in the United States from the I920s through the I980s. Public policy is viewed as shaped by officeholders\u27 ability to achieve political ends through augmenting information costs and other transaction costs facing the public. Public perceptions are seen both as the endogenous product of congressional information-cost manipulation and as an exogenous constraint that changes in identifiable ways over time. Different policy stances - open credit claiming, concealed credit claiming, early-stage blame avoidance, and full-scale blame avoidance - are predicted to emerge in response to specified conditions, yielding implications about the expected timing of public policy changes. Specific types of transaction-cost manipulation are predicted to accompany the identified policy stances. The US asbestos policy experience is shown to be consistent with the predictions of the model

Hydrogen-evolution-reaction kinetics pH dependence: Is it covered?

Writing in Joule, Surendranath and coworkers report intrinsic hydrogen-evolution-reaction activity and kinetic parameters for Pt and Au electrodes using "innocent” buffers that don't substantially affect electrode kinetics. A pH- and potential-dependent coverage of metal-H species is proposed to modulate apparent activity, findings that are important for a range of electrochemical technologies

Dynamics of Fe Adsorption and Desorption from CoO x H y During Oxygen Evolution Reaction Electrocatalysis

Iron plays a central and critical role in the water oxidation mechanism and the activity of transition-metal oxides and (oxy)hydroxides. Tracking Fe dynamics (deposition/dissolution/electrolyte transport) and unraveling the chemistries of various Fe active sites under oxygen-evolution reaction (OER) conditions are important for catalyst design, particularly for applications in alkaline electrolysis. Here, we use CoOxHy thin films as a platform to investigate Fe transport and reactivity at the catalyst-electrolyte interface and its impact on OER activity. We find that the deposition/dissolution of the surface-absorbed Fe species is governed by the transport of soluble Fe species and applied potential. Soluble Fe species in the electrolyte adsorb on CoOxHy under stirred electrolyte conditions. Accelerated Fe desorption is observed with a more-positive OER potential. The surface-localized Fe sites generated by absorption from soluble Fe species have a higher OER turnover frequency (TOFFe) compared to Fe in codeposited CoFeOxHy films. Operando X-ray absorption spectroscopy shows structural similarity between reference Fe oxyhydroxides and surface Fe sites on CoOxHy, contrasting with Fe sites within the CoOxHy structure made by codeposition, where Fe shows a different apparent X-ray absorption edge energy. The OER activity of the surface-absorbed Fe decreased by Fe desorption but was recoverable by redepositing Fe species under non-OER conditions

Purification of Residual Ni and Co Hydroxides from Fe‐Free Alkaline Electrolyte for Electrocatalysis Studies

It is critical to control Fe impurity concentrations in oxygen-evolution-reaction electrocatalysis experiments so that unambiguous assignments of activity and mechanistic details can be made. An established method to prepare Fe-free KOH electrolyte is by using particulate Ni(OH)2 or Co(OH)2 as absorbents to remove the Fe from KOH or other neutral-to-alkaline electrolytes. However, this method yields residual Ni or Co species in the electrolyte which can be redeposited on the working electrode. Thus, current methods of Fe removal could convolute studies of OER. In this work, we compared two different methods, continuous electrolysis and nano-filtration, to remove the Ni and/or Co species from Fe-free alkaline electrolyte. We found the best approach is to pass the Fe-free electrolyte through a hydrophilic 0.1 μm polyethersulfone filter which decreases the Ni species concentration in 1 M KOH to single ppb levels. This result suggests the remaining Ni or Co species are primarily particulate in nature, consistent with their small solubility as ions. In comparison, extended pre-electrolysis of the electrolyte removed only a portion of the Ni/Co

Oxygen Electrocatalysis on Mixed-Metal Oxides/Oxyhydroxides: From Fundamentals to Membrane Electrolyzer Technology

ConspectusCatalyzing the oxygen evolution reaction (OER) is important for key energy-storage technologies, particularly water electrolysis and photoelectrolysis for hydrogen fuel production. Under neutral-to-alkaline conditions, first-row transition-metal oxides/(oxy)hydroxides are the fastest-known OER catalysts and have been the subject of intense study for the past decade. Critical to their high performance is the intentional or accidental addition of Fe to Ni/Co oxides that convert to layered (oxy)hydroxide structures during the OER. Unraveling the role that Fe plays in the catalysis and the molecular identity of the true "active site" has proved challenging, however, due to the dynamics of the host structure and absorbed Fe sites as well as the diversity of local structures in these disordered active phases.In this Account, we highlight our work to understand the role of Fe in Ni/Co (oxy)hydroxide OER catalysts. We first discuss how we characterize the intrinsic activity of the first-row transition-metal (oxy)hydroxide catalysts as thin films by accounting for the contributions of the catalyst-layer thickness (mass loading) and electrical conductivity as well as the underlying substrate's chemical interactions with the catalyst and the presence of Fe species in the electrolyte. We show how Fe-doped Ni/Co (oxy)hydroxides restructure during catalysis, absorb/desorb Fe, and in some cases degrade or regenerate their activity during electrochemical testing. We highlight the relevant techniques and procedures that allowed us to better understand the role of Fe in activating other first-row transition metals for OER. We find several modes of Fe incorporation in Ni/Co (oxy)hydroxides and show how those modes correlate with activity and durability. We also discuss how this understanding informs the incorporation of earth-abundant transition-metal OER catalysts in anion-exchange-membrane water electrolyzers (AEMWE) that provide a locally basic anode environment but run on pure water and have advantages over the more-developed proton-exchange-membrane water electrolyzers (PEMWE) that use platinum-group-metal (PGM) catalysts. We outline the key issues of introducing Fe-doped Ni/Co (oxy)hydroxide catalysts at the anode of the AEMWE, such as the oxidative processes triggered by Fe species traveling through the polymer membrane, pH-gradient effects on the catalyst stability, and possibly limited catalyst utilization in the compressed stack configuration. We also suggest possible mitigation strategies for these issues. Finally, we summarize remaining challenges including the long-term stability of Fe-doped Ni/Co (oxy)hydroxides under OER conditions and the lack of accurate models of the dynamic active surface that hinder our understanding of, and thus ability to design, these catalysts

Trace Fe activates perovskite nickelate OER catalysts in alkaline media via redox-active surface Ni species formed during electrocatalysis

The accurate description of activity trends among perovskite-oxide oxygen-evolution-reaction (OER) catalysts using electronic-structure descriptors requires that the bulk structure of the catalyst is comparable to that of the surface. Few studies have addressed the dynamic nature of the catalyst's structure during the OER and the consequential implications for understanding activity. Here, we use a combination of electrochemical and materials-characterization techniques to study the surface reconstruction and the associated formation of a new redox-active phase on LaNiO3 particles, LaNiO3 epitaxial films, and an analogous Ruddlesden-Popper phase, La2NiO4. Small, but characteristic, redox features corresponding to Ni redox in nominally amorphous NiOxHy are observed during cyclic voltammetry of these initially fully crystalline materials. The size of these redox features grows with prolonged cycling and contributes to an increased surface area as determined from electrochemical impedance spectroscopy (EIS). We find the OER activity is strongly dependent on soluble Fe species in the electrolyte, common impurities in alkaline media. These observations are consistent with the reconstruction of the crystalline surface to form NiOxHy species and subsequent activation by adsorption of Fe forming the well-known and extremely active NiFeOxHy OER catalyst

Thin Cation-Exchange Layers Enable High-Current-Density Bipolar Membrane Electrolyzers via Improved Water Transport

With suitable water dissociation (WD) catalysts, bipolar membranes (BPMs) can efficiently dissociate water into H+ and OH- at the junction between anion- A nd cation-exchange layers (AEL and CEL, respectively). First, however, water must be transported through the AEL or CEL and thus against the outward flow of hydrated H+ and OH-. This is a challenge intrinsic to the BPM architecture and limits operation to current densities typically less than a0.5 A·cm-2. Here we explore how water transport affects durability and performance in reference alkaline and acidic membrane electrolyzers, and we use the insight gained to design BPMs with improved water transport. We demonstrate a thin-CEL BPM (2-μm Nafion CEL|a200 nm TiO2|a200 nm NiO + ionomer|50 μm Sustainion AEL) which maintains a pH difference of a14 units between the anode and cathode for current densities of up to 3.4 A·cm-2 with a total water electrolysis voltage of a4 V and an estimated WD overpotential of a1.5 V. Such high-current-density operation is crucial for key emerging BPM applications, including in water and carbon-dioxide electrolyzers and in (regenerative) fuel cells

Anode Catalysts in Anion‐Exchange‐Membrane Electrolysis without Supporting Electrolyte: Conductivity, Dynamics, and Ionomer Degradation

Anion-exchange-membrane water electrolyzers (AEMWEs) in principle operate without soluble electrolyte using earth-abundant catalysts and cell materials and thus lower the cost of green H2 . Current systems lack competitive performance and the durability needed for commercialization. One critical issue is a poor understanding of catalyst-specific degradation processes in the electrolyzer. While non-platinum-group-metal (non-PGM) oxygen-evolution catalysts show excellent performance and durability in strongly alkaline electrolyte, this has not transferred directly to pure-water AEMWEs. Here, AEMWEs with five non-PGM anode catalysts are built and the catalysts' structural stability and interactions with the alkaline ionomer are characterized during electrolyzer operation and post-mortem. The results show catalyst electrical conductivity is one key to obtaining high-performing systems and that many non-PGM catalysts restructure during operation. Dynamic Fe sites correlate with enhanced degradation rates, as does the addition of soluble Fe impurities. In contrast, electronically conductive Co3 O4 nanoparticles (without Fe in the crystal structure) yield AEMWEs from simple, standard preparation methods, with performance and stability comparable to IrO2 . These results reveal the fundamental dynamic catalytic processes resulting in AEMWE device failure under relevant conditions, demonstrate a viable non-PGM catalyst for AEMWE operation, and illustrate underlying design rules for engineering anode catalyst/ionomer layers with higher performance and durability