A pendant proton shuttle on [Fe4N(CO)12]- alters product selectivity in formate vs. H2 production via the hydride [H-Fe4N(CO)12].

Proton relays are known to increase reaction rates for H2 evolution and lower overpotentials in electrocatalytic reactions. In this report we describe two electrocatalysts, [Fe4N(CO)11(PPh3)]- (1-) which has no proton relay, and hydroxyl-containing [Fe4N(CO)11(Ph2P(CH2)2OH)]- (2-). Solid state structures indicate that these phosphine-substituted clusters are direct analogs of [Fe4N(CO)12]- where one CO ligand has been replaced by a phosphine. We show that the proton relay changes the selectivity of reactions: CO2 is reduced selectively to formate by 1- in the absence of a relay, and protons are reduced to H2 under a CO2 atmosphere by 2-. These results implicate a hydride intermediate in the mechanism of the reactions and demonstrate the importance of controlling proton delivery to control product selectivity. Thermochemical measurements performed using infrared spectroelectrochemistry provided pKa and hydricity values for [HFe4N(CO)11(PPh3)]-, which are 23.7, and 45.5 kcal mol-1, respectively. The pKa of the hydroxyl group in 2- was determined to fall between 29 and 41, and this suggests that the proximity of the proton relay to the active catalytic site plays a significant role in the product selectivity observed, since the acidity alone does not account for the observed results. More generally, this work emphasizes the importance of substrate delivery kinetics in determining the selectivity of CO2 reduction reactions that proceed through metal-hydride intermediates

Evidence for complete and partial surface renewal at an air-water interface

A wind-wave flume is used to determine the extent to which the thermal boundary layer (TBL) at a wind-forced air-water interface is completely renewed from below. We measure skin temperature, Tskin, radiometrically, temperature immediately below the TBL, Tsubskin, using a temperature profiler, and net heat flux using the gradient flux technique. The Tskin probability density function, p(Tskin), and surface renewal time scale, τ, were measured using passive and active infrared imaging techniques, respectively. We find that the mean percentile rank of Tsubskin in p(Tskin) is 99.90, implying that complete surface renewal occurs. This result suggests an alternative to radiometric measurement of Tskin through the simple combination of an infrared camera and an in situ temperature sensor. Comparison of the temperature difference across the TBL to the expected cooling implies that a significant portion of events only partially renew the TBL. This result should impact efforts to improve air-sea transfer models

SLAC/CERN high gradient tests on an X-band accelerating section

High frequency linear collider schemes envisage the use of rather high accelerating gradients: 50 to 100 MV/m for X-band and 80 MV/m for CLIC. Because these gradients are well above those commonly used in accelerators, high gradient studies of high frequency structures have been initiated and test facilities have been constructed at KEK [1], SLAC [2] and CERN [3]. The studies seek to demonstrate that the above mentioned gradients are both achievable and practical. There is no well-defined criterion for the maximum acceptable level of dark current but it must be low enough not to generate unacceptable transverse wakefields, disturb beam position monitor readings or cause RF power losses. Because there are of the order of 10,000 accelerating sections in a high frequency linear collider, the conditioning process should not be too long or difficult. The test facilities have been instrumented to allow investigation of field emission and RF breakdown mechanisms. With an understanding of these effects, the high gradient performance of accelerating sections may be improved through modifications in geometry, fabrication methods and surface finish. These high gradient test facilities also allow the ultimate performance of high frequency/short pulse length accelerating structures to be probed. This report describes the high gradient test at SLAC of an X-band accelerating section built at CERN using technology developed for CLIC

Extended sedimentation profiles in charged colloids: the gravitational length, entropy, and electrostatics

We have measured equilibrium sedimentation profiles in a colloidal model system with confocal microscopy. By tuning the interactions, we have determined the gravitational length in the limit of hard-sphere-like interactions, and using the same particles, tested a recent theory [R.van Roij, J. Phys. Cond. Mat. 15, S3569, (2003)], which predicts a significantly extended sedimentation profile in the case of charged colloids with long-ranged repulsions, due to a spontaneously formed macroscopic electric field. For the hard-sphere-like system we find that the gravitational length matches that expected. By tuning the buoyancy of the colloidal particles we have shown that a mean field hydrostatic equilibrium description even appears to hold in the case that the colloid volume fraction changes significantly on the length scale of the particle size. The extended sedimentation profiles of the colloids with long-ranged repulsions are well-described by theory. Surprisingly, the theory even seems to hold at concentrations where interactions between the colloids, which are not modeled explicitly, play a considerable role

Employing culturally responsive pedagogy to foster literacy learning in schools

 In recent years it has become increasingly obvious that, to enable students in schools from an increasingly diverse range of cultural backgrounds to acquire literacy to a standard that will support them to achieve academically, it is important to adopt pedagogy that is responsive to, and respectful of, them as culturally situated. What largely has been omitted from the literature, however, is discussion of a relevant model of learning to underpin this approach. For this reason this paper adopts a socio-cultural lens (Vygotsky, 1978) through which to view such pedagogy and refers to a number of seminal texts to justify of its relevance. Use of this lens is seen as having a particular rationale. It forces a focus on the agency of the teacher as a mediator of learning who needs to acknowledge the learner’s cultural situatedness (Kozulin, 2003) if school literacy learning for all students is to be as successful as it might be. It also focuses attention on the predominant value systems and social practices that characterize the school settings in which students’ literacy learning is acquired. The paper discusses implications for policy and practice at whole-school, classroom and individual student levels of culturally-responsive pedagogy that is based on a socio-cultural model of learning. In doing so it draws on illustrations from the work of a number of researchers, including that of the author