Operando probing of the surface chemistry during the Haber-Bosch process.

The large-scale conversion of N2 and H2 into NH3 (refs. 1,2) over Fe and Ru catalysts3 for fertilizer production occurs through the Haber-Bosch process, which has been considered the most important scientific invention of the twentieth century4. The active component of the catalyst enabling the conversion was variously considered to be the oxide5, nitride2, metallic phase or surface nitride6, and the rate-limiting step has been associated with N2 dissociation7-9, reaction of the adsorbed nitrogen10 and also NH3 desorption11. This range of views reflects that the Haber-Bosch process operates at high temperatures and pressures, whereas surface-sensitive techniques that might differentiate between different mechanistic proposals require vacuum conditions. Mechanistic studies have accordingly long been limited to theoretical calculations12. Here we use X-ray photoelectron spectroscopy-capable of revealing the chemical state of catalytic surfaces and recently adapted to operando investigations13 of methanol14 and Fischer-Tropsch synthesis15-to determine the surface composition of Fe and Ru catalysts during NH3 production at pressures up to 1 bar and temperatures as high as 723 K. We find that, although flat and stepped Fe surfaces and Ru single-crystal surfaces all remain metallic, the latter are almost adsorbate free, whereas Fe catalysts retain a small amount of adsorbed N and develop at lower temperatures high amine (NHx) coverages on the stepped surfaces. These observations indicate that the rate-limiting step on Ru is always N2 dissociation. On Fe catalysts, by contrast and as predicted by theory16, hydrogenation of adsorbed N atoms is less efficient to the extent that the rate-limiting step switches following temperature lowering from N2 dissociation to the hydrogenation of surface species.

Demonstrating Pressure Jumping as a Tool to Address the Pressure Gap in High Pressure Photoelectron Spectroscopy of CO and CO2 Hydrogenation on Rh(211).

Operando probing by x-ray photoelectron spectroscopy (XPS) of certain hydrogenation reactions are often limited by the scattering of photoelectrons in the gas phase. This work describes a method designed to partially circumvent this so called pressure gap. By performing a rapid switch from a high pressure (where acquisition is impossible) to a lower pressure we can for a short while probe a "remnant" of the high pressure surface as well as the time dynamics during the re-equilibration to the new pressure. This methodology is demonstrated using the CO2 and the CO hydrogenation reaction over Rh(211). In the CO2 hydrogenation reaction, the remnant surface of a 2 bar pressure shows an adsorbate distribution which favors chemisorbed CHx adsorbates over chemisorbed CO. This contrasts against previous static operando spectra acquired at lower pressures. Furthermore, the pressure jumping method yields a faster acquisition and more detailed spectra than static operando measurements above 1 bar. In the CO hydrogenation reaction, we observe that CHx accumulated faster during the 275 mbar low pressure regime, and different hypotheses are presented regarding this observation.

Multi-spectroscopic study of electrochemically-formed oxide-derived gold electrodes.

Oxide-derived metals are produced by reducing an oxide precursor. These materials, including gold, have shown improved catalytic performance over many native metals. The origin of this improvement for gold is not yet understood. In this study, operando non-resonant sum frequency generation (SFG) and ex situ high-pressure X-ray photoelectron spectroscopy (HP-XPS) have been employed to investigate electrochemically-formed oxide-derived gold (OD-Au) from polycrystalline gold surfaces. A range of different oxidizing conditions were used to form OD-Au in acidic aqueous medium (H3PO4, pH = 1). Our electrochemical data after OD-Au is generated suggest that the surface is metallic gold, however SFG signal variations indicate the presence of subsurface gold oxide remnants between the metallic gold surface layer and bulk gold. The HP-XPS results suggest that this subsurface gold oxide could be in the form of Au2O3 or Au(OH)3. Furthermore, the SFG measurements show that with reducing electrochemical treatments the original gold metallic state can be restored, meaning the subsurface gold oxide is released. This work demonstrates that remnants of gold oxide persist beneath the topmost gold layer when the OD-Au is created, potentially facilitating the understanding of the improved catalytic properties of OD-Au.

Operando Observation of Oxygenated Intermediates during CO Hydrogenation on Rh Single Crystals.

The CO hydrogenation reaction over the Rh(111) and (211) surfaces has been investigated operando by X-ray photoelectron spectroscopy at a pressure of 150 mbar. Observations of the resting state of the catalyst give mechanistic insight into the selectivity of Rh for generating ethanol from CO hydrogenation. This study shows that the Rh(111) surface does not dissociate all CO molecules before hydrogenation of the O and C atoms, which allows methoxy and other both oxygenated and hydrogenated species to be visible in the photoelectron spectra.

Norm proximity and optimal social comparisons for energy conservation behavior.

Bottom-up solutions targeting individual energy conservation behaviors can play an important role in mitigating climate change and other environmental problems. Information interventions using social comparisons have proven generally effective at improving conservation behaviors, yet are largely suboptimal and sometimes fail when not adequately designed for their specific context. Environmental managers and policy makers need guidance on behavioral intervention design to maximize effectiveness. This article reports the results of a randomized control trial field experiment that used social comparisons to influence individual electricity conservation behaviors in a unique experimental setting with homogeneous residential units and no economic incentive for subjects to conserve. Two treatment groups receiving information feedback with different social comparison reference points exhibited an average treatment effect of 6 % relative to a control group that did not receive feedback. Moreover, treated subjects whose baseline behavior was more proximate to their relevant comparison group norm exhibited stronger response to the treatment (greater than 10 %) than treated subjects whose baseline behavior was more distant from the relevant norm. These results demonstrate that individuals may be more responsive to social norms when provided with a relevant norm that is more proximate to their baseline behavior. Our findings have important practical implications for optimal design and implementation of behavioral interventions to improve environmental management and achieve energy policy goals.

The IκB Kinases Restrict Human Cytomegalovirus Infection.

Human cytomegalovirus (HCMV) is a ubiquitous herpesvirus that causes disease in immunosuppressed populations. HCMV has a complex relationship with innate immune signaling pathways. Specifically, HCMV has been found to block some aspects of inflammatory signaling while benefiting from others. Through analysis of knockout cell lines targeting the NF-κB regulatory kinases IκB kinase α (IKKα) and IKKß, we find that the IKKs are host restriction factors that contribute to cytokine-mediated resistance to viral infection, limit the initiation of HCMV infection, and attenuate viral cell-to-cell spread. The HCMV UL26 protein is a viral immune modulator important for HCMV infection that has been shown to inhibit host cell NF-κB signaling, yet it has remained unclear how UL26-mediated NF-κB modulation contributes to infection. Here, we find that UL26 modulation of NF-κB signaling is separable from its contribution to high-titer viral replication. However, we find that IKKß is required for the induction of cytokine expression associated with ΔUL26 infection. Collectively, our data indicate that the IKKs restrict infection but HCMV targets their signaling to modulate the cellular inflammatory environment.IMPORTANCE Innate immune signaling is a critical defense against viral infection and represents a central host-virus interaction that frequently determines the outcomes of infections. NF-κB signaling is an essential component of innate immunity that is extensively modulated by HCMV, a significant cause of morbidity in neonates and immunosuppressed individuals. However, the roles that various facets of NF-κB signaling play during HCMV infection have remained elusive. We find that the two major regulatory kinases in this pathway, IKKα and IKKß, limit the initiation of infection, viral replication, and cell-to-cell spread. In addition, our results indicate that these kinases contribute differently to the host cell response to infection in the absence of a virally encoded NF-κB inhibitor, UL26. Given the importance of NF-κB in viral infection, elucidating the contributions of various NF-κB constituents to infection is an essential first step toward the possibility of targeting this pathway therapeutically.

UL26 Attenuates IKKß-Mediated Induction of Interferon-Stimulated Gene (ISG) Expression and Enhanced Protein ISGylation during Human Cytomegalovirus Infection.

Viruses must negotiate cellular antiviral responses in order to replicate. Human cytomegalovirus (HCMV) is a prevalent betaherpesvirus that encodes a number of viral gene products that modulate cellular antiviral signaling. The HCMV UL26 gene has previously been found to attenuate cytokine-activated NF-κB signaling, yet the role that UL26 plays in modulating the host cell's global transcriptional response to infection is not clear. Here, we find that infection with a UL26 deletion virus (ΔUL26) induces a proinflammatory transcriptional environment that includes substantial increases in the expression of cytokine signaling genes relative to wild-type HCMV. These increases include NF-κB-regulated genes as well as interferon-stimulated genes (ISGs), such as ISG15 and bone marrow stromal cell antigen 2 (BST2). The ΔUL26 mutant-mediated induction of ISG15 expression was found to drive increases in global protein ISGylation during ΔUL26 mutant infection. However, short hairpin RNA (shRNA) and CRISPR-mediated targeting of ISG15 indicated that its induction does not restrict HCMV infection. In contrast, shRNA-mediated targeting of BST2 demonstrated that BST2 restricts HCMV cell-to-cell spread. In addition, the increased expression of both of these ISGs and the global enhancement in protein ISGylation were found to be dependent on the activity of the canonical inhibitor of NF-κB kinase beta (IKKß). Both CRISPR-based and pharmacologically mediated inhibition of IKKß blocked the induction of ISG15 and BST2. These results suggest significant cross-talk between the NF-κB and interferon signaling pathways and highlight the importance of IKK signaling and the HCMV UL26 protein in shaping the antiviral response to HCMV.IMPORTANCE Modulation of cellular antiviral signaling is a key determinant of viral pathogenesis. Human cytomegalovirus (HCMV) is a significant source of morbidity in neonates and the immunosuppressed that contains many genes that modulate antiviral signaling, yet how these genes contribute to shaping the host cell's transcriptional response to infection is largely unclear. Our results indicate that the HCMV UL26 protein is critical in preventing the establishment of a broad cellular proinflammatory transcriptional environment. Further, we find that the host gene IKKß is an essential determinant governing the host cell's antiviral transcriptional response. Given their importance to viral pathogenesis, continuing to elucidate the functional interactions between viruses and the cellular innate immune response could enable the development of therapeutic strategies to limit viral infection.

Impacts of hydrous manganese oxide on the retention and lability of dissolved organic matter.

Minerals constitute a primary ecosystem control on organic C decomposition in soils, and therefore on greenhouse gas fluxes to the atmosphere. Secondary minerals, in particular, Fe and Al (oxyhydr)oxides-collectively referred to as "oxides" hereafter-are prominent protectors of organic C against microbial decomposition through sorption and complexation reactions. However, the impacts of Mn oxides on organic C retention and lability in soils are poorly understood. Here we show that hydrous Mn oxide (HMO), a poorly crystalline δ-MnO2, has a greater maximum sorption capacity for dissolved organic matter (DOM) derived from a deciduous forest composite Oi, Oe, and Oa horizon leachate ("O horizon leachate" hereafter) than does goethite under acidic (pH 5) conditions. Nonetheless, goethite has a stronger sorption capacity for DOM at low initial C:(Mn or Fe) molar ratios compared to HMO, probably due to ligand exchange with carboxylate groups as revealed by attenuated total reflectance-Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy and scanning transmission X-ray microscopy-near-edge X-ray absorption fine structure spectroscopy coupled with Mn mass balance calculations reveal that DOM sorption onto HMO induces partial Mn reductive dissolution and Mn reduction of the residual HMO. X-ray photoelectron spectroscopy further shows increasing Mn(II) concentrations are correlated with increasing oxidized C (C=O) content (r = 0.78, P < 0.0006) on the DOM-HMO complexes. We posit that DOM is the more probable reductant of HMO, as Mn(II)-induced HMO dissolution does not alter the Mn speciation of the residual HMO at pH 5. At a lower C loading (2 × 102 µg C m-2), DOM desorption-assessed by 0.1 M NaH2PO4 extraction-is lower for HMO than for goethite, whereas the extent of desorption is the same at a higher C loading (4 × 102 µg C m-2). No significant differences are observed in the impacts of HMO and goethite on the biodegradability of the DOM remaining in solution after DOM sorption reaches steady state. Overall, HMO shows a relatively strong capacity to sorb DOM and resist phosphate-induced desorption, but DOM-HMO complexes may be more vulnerable to reductive dissolution than DOM-goethite complexes.

Gas-cluster ion sputtering: Effect on organic layer morphology.

Analysis of the surface of thin Irganox 1010 films before and after sputtering with an argon gas-cluster ion beam was performed with AFM and XPS to determine the effect that Zalar rotation has on the chemistry and morphology of the surface. The analysis is based on the change in roughness of the surface by comparing the same location on the surface before and after sputtering. The ion beam used was an Arn+ of size n = 1000 and energy 4 keV. The XPS analysis agreed with previous results in which the ion beam did not cause measurable accumulation of damaged material. Based on the AFM results, the Irganox 1010 surface became rougher as a result of ion sputtering, and the degree of roughening was quantified, as was the sputter rate. Furthermore, Zalar rotation during ion sputtering did not have a significant effect on surface roughening, surprisingly.

In Situ Surface-Sensitive Investigation of Multiple Carbon Phases on Fe(110) in the Fischer-Tropsch Synthesis.

Carbide formation on iron-based catalysts is an integral and, arguably, the most important part of the Fischer-Tropsch synthesis process, converting CO and H2 into synthetic fuels and numerous valuable chemicals. Here, we report an in situ surface-sensitive study of the effect of pressure, temperature, time, and gas feed composition on the growth dynamics of two distinct iron-carbon phases with the octahedral and trigonal prismatic coordination of carbon sites on an Fe(110) single crystal acting as a model catalyst. Using a combination of state-of-the-art X-ray photoelectron spectroscopy at an unprecedentedly high pressure, high-energy surface X-ray diffraction, mass spectrometry, and theoretical calculations, we reveal the details of iron surface carburization and product formation under semirealistic conditions. We provide a detailed insight into the state of the catalyst's surface in relation to the reaction.

The state of zinc in methanol synthesis over a Zn/ZnO/Cu(211) model catalyst.

The active chemical state of zinc (Zn) in a zinc-copper (Zn-Cu) catalyst during carbon dioxide/carbon monoxide (CO2/CO) hydrogenation has been debated to be Zn oxide (ZnO) nanoparticles, metallic Zn, or a Zn-Cu surface alloy. We used x-ray photoelectron spectroscopy at 180 to 500 millibar to probe the nature of Zn and reaction intermediates during CO2/CO hydrogenation over Zn/ZnO/Cu(211), where the temperature is sufficiently high for the reaction to rapidly turn over, thus creating an almost adsorbate-free surface. Tuning of the grazing incidence angle makes it possible to achieve either surface or bulk sensitivity. Hydrogenation of CO2 gives preference to ZnO in the form of clusters or nanoparticles, whereas in pure CO a surface Zn-Cu alloy becomes more prominent. The results reveal a specific role of CO in the formation of the Zn-Cu surface alloy as an active phase that facilitates efficient CO2 methanol synthesis.

A Novel Method to Maintain the Sample Position and Pressure in Differentially Pumped Systems Below the Resolution Limit of Optical Microscopy Techniques.

We present a new method to maintain constant gas pressure over a sample during in situ measurements. The example shown here is a differentially pumped high-pressure X-ray photoelectron spectroscopy system, but this technique could be applied to many in situ instruments. By using the pressure of the differential stage as a feedback source to change the sample position, a new level of consistency has been achieved. Depending on the absolute value of the sample-to-aperture distance, this technique allows one to maintain the distance within several hundred nanometers, which is below the limit of typical optical microscopy systems. We show that this method is well suited to compensate for thermal drift. Thus, X-ray photoelectron spectroscopy data can be acquired continuously while the sample is heated and maintaining constant pressure over the sample. By implementing a precise manipulator feedback system, pressure variations of less than 5% were reached while the temperature was varied by 400 ℃. The system is also shown to be highly stable under significant changes in gas flow. After changing the flow by a factor of two, the pressure returned to the set value within 60 s.

Bridging the Pressure Gap in CO Oxidation.

Performing fundamental operando catalysis studies under realistic conditions is a key to further develop and increase the efficiency of industrial catalysts. Operando X-ray photoelectron spectroscopy (XPS) experiments have been limited to pressures, and the relevance for industrial applications has been questioned. Herein, we report on the CO oxidation experiment on Pd(100) performed at a total pressure of 1 bar using XPS. We investigate the light-off regime and the surface chemical composition at the atomistic level in the highly active phase. Furthermore, the observed gas-phase photoemission peaks of CO2, CO, and O2 indicate that the kinetics of the reaction during the light-off regime can be followed operando, and by studying the reaction rate of the reaction, the activation energy is calculated. The reaction was preceded by an in situ oxidation study in 7% O2 in He and a total pressure of 70 mbar to confirm the surface sensitivity and assignment of the oxygen-induced photoemission peaks. However, oxygen-induced photoemission peaks were not observed during the reaction studies, but instead, a metallic Pd phase is present in the highly active regime under the conditions applied. The novel XPS setup utilizes hard X-rays to enable high-pressure studies, combined with a grazing incident angle to increase the surface sensitivity of the measurement. Our findings demonstrate the possibilities of achieving chemical information of the catalyst, operando, on an atomistic level, under industrially relevant conditions.

The Structure of the Active Pd State During Catalytic Carbon Monoxide Oxidization.

Using grazing incidence X-rays and X-ray photoelectron spectroscopy during the mass transfer limited catalytic oxidation of CO, the long-range surface structure of Pd(100) was investigated. Under the reaction conditions of 50:4 O2 to CO, 300 mbar pressure, and temperatures between 200 and 450 °C, the surface structure resulting from oxidation and the subsequent oxide reduction was elucidated. The reduction cycle was halted, and while under reaction conditions, angle-dependent X-ray photoelectron spectroscopy close to the critical angle of Pd and modeling of the data was performed. Two proposed models for the system were compared. The suggestion with the metallic islands formed on top of the oxide island was shown to be consistent with the data.

Stroboscopic operando spectroscopy of the dynamics in heterogeneous catalysis by event-averaging.

Heterogeneous catalyst surfaces are dynamic entities that respond rapidly to changes in their local gas environment, and the dynamics of the response is a decisive factor for the catalysts' action and activity. Few probes are able to map catalyst structure and local gas environment simultaneously under reaction conditions at the timescales of the dynamic changes. Here we use the CO oxidation reaction and a Pd(100) model catalyst to demonstrate how such studies can be performed by time-resolved ambient pressure photoelectron spectroscopy. Central elements of the method are cyclic gas pulsing and software-based event-averaging by image recognition of spectral features. A key finding is that at 3.2 mbar total pressure a metallic, predominantly CO-covered metallic surface turns highly active for a few seconds once the O2:CO ratio becomes high enough to lift the CO poisoning effect before mass transport limitations triggers formation of a √5 oxide.

On the origins of diastereoselectivity in the alkylation of enolates derived from N-1-(1'-naphthyl)ethyl-O-tert-butylhydroxamates: chiral Weinreb amide equivalents.

The stereochemical outcome observed upon alkylation of enolates derived from N-1-(1'-naphthyl)ethyl-O-tert-butylhydroxamates (chiral Weinreb amide equivalents) may be rationalized by a chiral relay mechanism. Deprotonation with KHMDS leads to a nonchelated (Z)-enolate in which the oxygen atoms adopt an anti-periplanar conformation. The configuration of the N-1-(1'-naphthyl)ethyl group dictates the conformation of the O-tert-butyl group and the configuration adopted by the adjacent pyramidal nitrogen atom. Highly diastereoselective enolate alkylation then proceeds anti to both the bulky tert-butyl group (sterically driven) and the N-lone pair (stereoelectronically driven).

Quantification and molecular characterization of organo-mineral associations as influenced by redox oscillations.

Organo-mineral association is one of the most important stabilization mechanisms of soil organic matter. However, few studies have been conducted to assess the retention, transformation, and transportation of colloids (1-1000 nm) and associated organic carbon (OC) in soil. Given the particularly significant role that wetland soils play in carbon storage and cycling, we quantified the dynamics of organo-mineral association within colloidal size range by conducting three consecutive 35-day redox (reduction-oxidation) oscillation experiments using a wetland soil. Molecular compositions of natural nanoparticle (NNP, 2.3-100 nm), fine colloid (100-450 nm), and particulate (450-1000 nm) fractions were measured using isotope ratio mass spectrometry (IRMS) and x-ray photoelectron spectroscopy (XPS). Results showed that NNP and fine colloids constituted up to 8.94 ± 0.50% and 22.19 ± 7.52% of bulk C concentration (2.3-1000 nm), respectively; indicating substantial contributions of these two fractions to the operationally defined "dissolved" (<450 nm) fraction. There was significant enrichment in heavier δ13C isotopes (p < 0.001) with size: NNP (-29.64 ± 0.32‰) < fine colloid (-28.81 ± 0.31‰) < particulate (-28.34 ± 0.25‰) fractions. NNP had the highest percentages of carbonyl/carboxyl C (C=O); while fine colloid and particulate fractions contained more reduced aromatic or aliphatic C (C-C, C=C, C-H). OC became more enriched (‰) in microbial-derived C (higher δ13C) with increasing particle size as well as with repeated redox oscillations. Our findings clearly demonstrate limitations of using the operationally defined "dissolved" fraction (<450 nm) to assess C cycling in ecosystems such as wetlands. Increase in colloid and OC concentrations and presence of more microbial-derived C in larger size fractions additionally imply that redox oscillations promote the formation of molecularly diverse sub-colloid sized organo-mineral associations. Being a composite unit of soil microaggregates, organic-mineral associations can thus influence the overall stability of OC in wetland soils that undergo frequent redox oscillations.

Who's Driving? Human Cytomegalovirus, Interferon, and NFκB Signaling.

As essential components of the host's innate immune response, NFκB and interferon signaling are critical determinants of the outcome of infection. Over the past 25 years, numerous Human Cytomegalovirus (HCMV) genes have been identified that antagonize or modulate the signaling of these pathways. Here we review the biology of the HCMV factors that alter NFκB and interferon signaling, including what is currently known about how these viral genes contribute to infection and persistence, as well as the major outstanding questions that remain.

Stealing the Keys to the Kitchen: Viral Manipulation of the Host Cell Metabolic Network.

Host cells possess the metabolic assets required for viral infection. Recent studies indicate that control of the host's metabolic resources is a core host-pathogen interaction. Viruses have evolved mechanisms to usurp the host's metabolic resources, funneling them towards the production of virion components as well as the organization of specialized compartments for replication, maturation, and dissemination. Consequently, hosts have developed a variety of metabolic countermeasures to sense and resist these viral changes. The complex interplay between virus and host over metabolic control has only just begun to be deconvoluted. However, it is clear that virally induced metabolic reprogramming can substantially impact infectious outcomes, highlighting the promise of targeting these processes for antiviral therapeutic development.