title: An X-ray absorption spectroscopy investigation of the coordination environment of electrogenerated Ni(ii)-pseudohalide complexes arising from the anodic polarization of Ni electrodes in DMSO solutions of NCO⁻ , NCS⁻ and NCSe⁻ ions

authors: Alwis, Kethsiri H.K.L.

subjects: EXAFS/XANES

abstract: X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) were used to provide direct information in solution on the coordination state of electrogenerated products from anodically polarized nickel electrodes in pseudohalide-ion-containing dimethyl sulfoxide (DMSO) solvent (i.e. NCX⁻, X = O, S, Se) in the presence of a supporting electrolyte of tetrabutylammonium perchlorate (TBAP). Electrogenerated solutions and model solutions representative of the chemical speciation in electrolyzed systems (prepared by mixing Ni(II) and pseudohalide ion solutions in DMSO), were also examined. In general for Ni(II) interacting with NCS⁻ and NCSe⁻, the complex ion generated appears to be 6-coordinate [Ni(NCX)(DMSO)5]⁺, while EXAFS/XANES data of the Ni/cyanate system suggest an average coordination number of 5, which in reality is due to the electrogenerated solution containing a mixture of 4 coordinate (tetrahedral) [Ni(NCO)4]²⁻ and octahedral [Ni(DMSO)6]²⁺ species. These observations of the octahedral geometry for the Ni(II)/thiocyanate and Ni(II)/selenocyanate systems and 5-coordinate geometry in the Ni(II)/cyanate systems (being electrogenerated products of anodic polarisation of Ni in the DMSO-supported pseudohalide ion electrolytes) agree with the differences in colour observed between samples. EXAFS/XANES measurements combined with IR spectroelectrochemical analyses of solutions provide a versatile way of analyzing these electrochemical systems without the need for isolating compounds from the electrolyte.

text: An X-ray absorption spectroscopy investigation of the coordination environment of electrogenerated Ni(ii)-pseudohalide complexes arising from the anodic polarization of Ni electrodes in DMSO solutions of NCO⁻ , NCS⁻ and NCSe⁻ ions X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) were used to provide direct information in solution on the coordination state of electrogenerated products from anodically polarized nickel electrodes in pseudohalide-ion-containing dimethyl sulfoxide (DMSO) solvent (i.e. NCX⁻, X = O, S, Se) in the presence of a supporting electrolyte of tetrabutylammonium perchlorate (TBAP). Electrogenerated solutions and model solutions representative of the chemical speciation in electrolyzed systems (prepared by mixing Ni(II) and pseudohalide ion solutions in DMSO), were also examined. In general for Ni(II) interacting with NCS⁻ and NCSe⁻, the complex ion generated appears to be 6-coordinate [Ni(NCX)(DMSO)5]⁺, while EXAFS/XANES data of the Ni/cyanate system suggest an average coordination number of 5, which in reality is due to the electrogenerated solution containing a mixture of 4 coordinate (tetrahedral) [Ni(NCO)4]²⁻ and octahedral [Ni(DMSO)6]²⁺ species. These observations of the octahedral geometry for the Ni(II)/thiocyanate and Ni(II)/selenocyanate systems and 5-coordinate geometry in the Ni(II)/cyanate systems (being electrogenerated products of anodic polarisation of Ni in the DMSO-supported pseudohalide ion electrolytes) agree with the differences in colour observed between samples. EXAFS/XANES measurements combined with IR spectroelectrochemical analyses of solutions provide a versatile way of analyzing these electrochemical systems without the need for isolating compounds from the electrolyte.

year: 2015

title: Multiple frequency range imaging to remove measurement ambiguity

authors: Payne, Andrew D.

subjects: range imaging system

abstract: Range imaging systems use a specialised sensor to capture an image where object distance (range) is measured for every pixel using time-of-flight. The scene is illuminated with an amplitude modulated light source, and the phase of the modulation envelope of the reflected light is measured to determine flight time, hence object distance for each pixel. As the modulation waveform is cyclic, an ambiguity problem exists if the phase shift exceeds 2π radians. To overcome this problem we demonstrate a method that superposes two different modulation frequencies within a single capture. This technique reduces the associated overhead compared with performing two sequential measurements, allowing the system to retain high range measurement precision at rapid acquisition rates. A method is also provided to avoid interference from aliased harmonics during sampling, which otherwise contaminate the resulting range measurement. Experimental results show the potential of the multiple frequency approach; producing high measurement precision while avoiding ambiguity. The results also demonstrate the limitation of this technique, where large errors can be introduced through a combination of a low signal to noise ratio and suboptimal selection of system parameters.

text: Multiple frequency range imaging to remove measurement ambiguity Range imaging systems use a specialised sensor to capture an image where object distance (range) is measured for every pixel using time-of-flight. The scene is illuminated with an amplitude modulated light source, and the phase of the modulation envelope of the reflected light is measured to determine flight time, hence object distance for each pixel. As the modulation waveform is cyclic, an ambiguity problem exists if the phase shift exceeds 2π radians. To overcome this problem we demonstrate a method that superposes two different modulation frequencies within a single capture. This technique reduces the associated overhead compared with performing two sequential measurements, allowing the system to retain high range measurement precision at rapid acquisition rates. A method is also provided to avoid interference from aliased harmonics during sampling, which otherwise contaminate the resulting range measurement. Experimental results show the potential of the multiple frequency approach; producing high measurement precision while avoiding ambiguity. The results also demonstrate the limitation of this technique, where large errors can be introduced through a combination of a low signal to noise ratio and suboptimal selection of system parameters.

year: 2009

title: Participatory data design: managing data sovereignty in IoT solutions

authors: Bowen, Judy

subjects: computer science

abstract: Within the software engineering community, deciding how to collect, store and use personal data has become about more than just understanding our users. This paper considers ethical data use which includes cultural considerations and data ownership rights. We discuss indigenous data sovereignty as a concept and how it potentially impacts technological solutions that gather personal data from users. We propose an extension to typical user-centred design processes which we call participatory data design. This incorporates the use of frameworks and tools that specifically focus on managing data within the cultural context it is gathered from. We also present a specific example of how we have used this approach in the context of a data collection project from M¯aori workers in New Zealand forestry. We conclude with a discussion of the wider implications of this approach.

text: Participatory data design: managing data sovereignty in IoT solutions Within the software engineering community, deciding how to collect, store and use personal data has become about more than just understanding our users. This paper considers ethical data use which includes cultural considerations and data ownership rights. We discuss indigenous data sovereignty as a concept and how it potentially impacts technological solutions that gather personal data from users. We propose an extension to typical user-centred design processes which we call participatory data design. This incorporates the use of frameworks and tools that specifically focus on managing data within the cultural context it is gathered from. We also present a specific example of how we have used this approach in the context of a data collection project from M¯aori workers in New Zealand forestry. We conclude with a discussion of the wider implications of this approach.

year: 2022