Copper and Copper Alloy Electrocatalysts for the Conversion of Carbon Dioxide to Fuels

The electrochemical CO₂ reduction reaction (CO₂RR) can couple carbon sequestration with renewable energy to convert CO₂ into chemical feedstocks. For this process, copper is the only metal known to catalyze the CO₂RR to hydrocarbons with adequate efficiency but suffers from poor selectivity. Copper-based alloys and bi-metallic materials show improved CO₂ reduction selectivity compared to copper and the secondary element likely plays an important role. However, justification for the intrinsic effects of the secondary element on the catalytic mechanism and resultant selectivity is lacking. Therefore, the goal of this Thesis is to investigate how the selectivity of these copper-based systems are improved by the secondary elements. An understanding of their effects on the catalytic mechanism is gained through a combination of electrochemistry, in-situ spectroscopy, theoretical computations, and material characterization techniques. In this Thesis, copper-tin alloys are studied and found to exhibit high selectivities towards CO and formate. As the tin concentration increases, a composition-dependent selectivity trend is observed, which is accompanied by a shift in intermediate binding preference of the first reaction intermediate. The binding configurations of this intermediate, either carbon-bound *COOH or oxygen-bound *OCHO, are identified using in-situ Raman spectroscopy. Theoretical computations also identify a gradual weakening of *COOH adsorption and strengthening of *OCHO adsorption with increasing tin concentration. This behavior is explained by the resultant charge redistribution which occurs from alloying. Consequently, local positive charge on the tin sites hinders nucleophilic attack of the carbon in the CO2 molecule and preferences *OCHO adsorption in the first reaction step. In-situ spectroscopy is further applied to study copper-based systems and their selectivities towards C2 products. Iodide-derived copper (ID-Cu) exhibits significantly greater ethane selectivity and more favorable kinetics compared to oxide-derived copper (OD-Cu). A key intermediate in the ethane mechanism is identified by in-situ X-ray adsorption and Raman spectroscopies and is likely better stabilized on ID-Cu due to its trace iodine species. It is also postulated that the ability of a catalyst to bind this intermediate determines the selectivity towards either ethane or ethanol in the C2 pathway. Using in-situ ATR-FTIR to study OD-Cu nanocubes, bridge-bonded *CO is found to be the dominant binding mode of CO at overpotentials relevant to C2 product generation. However, OD-Cu nanocubes with electrodeposited gold (OD-Cu-Au) achieve a higher selectivity for ethylene and maintain a higher population of linearbonded *CO at these overpotentials. From these in-situ studies, it is demonstrated how the secondary element can affect the adsorption energetics of key reaction intermediates and improve the selectivity of copper-based electrocatalysts.Thesis (Ph.D.) -- University of Adelaide, School of Chemical Engineering and Advanced Materials, 202

Rationally designed transition metal hydroxide nanosheet arrays on graphene for artificial CO2 reduction

The performance of transition metal hydroxides, as cocatalysts for CO2 photoreduction, is significantly limited by their inherent weaknesses of poor conductivity and stacked structure. Herein, we report the rational assembly of a series of transition metal hydroxides on graphene to act as a cocatalyst ensemble for efficient CO2 photoreduction. In particular, with the Ru-dye as visible light photosensitizer, hierarchical Ni(OH)2 nanosheet arrays-graphene (Ni(OH)2-GR) composites exhibit superior photoactivity and selectivity, which remarkably surpass other counterparts and most of analogous hybrid photocatalyst system. The origin of such superior performance of Ni(OH)2-GR is attributed to its appropriate synergy on the enhanced adsorption of CO2, increased active sites for CO2 reduction and improved charge carriers separation/transfer. This work is anticipated to spur rationally designing efficient earth-abundant transition metal hydroxides-based cocatalysts on graphene and other two-dimension platforms for artificial reduction of CO2 to solar chemicals and fuels

Non-medical prescribing versus medical prescribing for acute and chronic disease management in primary and secondary care.

The aim of this Cochrane review was to find out if prescribing by health professionals other than doctors delivers comparable outcomes to prescribing by doctors. Cochrane researchers collected and analysed all relevant studies to answer this question and found 46 studies. Key messages With appropriate training and support, nurses and pharmacists are able to prescribe medicines as part of managing a range of conditions to achieve comparable health management outcomes to doctors. The majority of studies focus on chronic disease management in higher-income counties where there is generally a moderate-certainty of evidence supporting similar outcomes for the markers of disease in high blood pressure, diabetes, and high cholesterol. Further high-quality studies are needed in poorer countries and to better quantify differences in prescribing outcomes for adverse events, and to determine health economic outcomes. Further studies could also focus more specifically on the prescribing component of care. What was studied in the review? A number of countries allow health professionals other than doctors to prescribe medicines. This shift in roles is thought to provide improved and timely access to medicines for consumers where there are shortages of doctors or the health system is facing pressures in coping with the burden of disease. In addition, this task shift has been supported by a number of governments as a way to more appropriately use the skills of health professionals, such as nurses and pharmacists, in the care of patients. We compared the outcomes of any healthcare workers who were prescribing with a high degree of autonomy with medical prescribers in the hospital or community setting in low-, middle- and high-income countries. What are the main results of the review? This review found 45 studies where nurses and pharmacists with high levels of prescribing autonomy were compared with usual care medical prescribers. A further study compared nurse prescribing with guideline support with usual nurse prescribing care. No studies were found with other health professionals or lay prescribers. Four nurse prescribing studies were undertaken in the low- and middle-income settings of Colombia, South Africa, Uganda, and Thailand. The remainder of studies were undertaken in high-income Western countries. Forty-two studies were based in a community setting, two studies were located in hospitals, one study in the workplace, and one study in an aged care facility. Prescribing was but one part of many health-related interventions, particularly in the management of chronic disease. The review found that the outcomes for non-medical prescribers were comparable to medical prescribers for: high blood pressure (moderate-certainty of evidence); diabetes control (high-certainty of evidence); high cholesterol (moderate-certainty of evidence); adverse events (low-certainty of evidence); patients adhering to their medication regimeans (moderate-certainty of evidence); patient satisfaction with care (moderate-certainty of evidence); and health-related quality of life (moderate-certainty of evidence). Pharmacists and nurses with varying levels of undergraduate, postgraduate, and specific on-the-job training related to the disease or condition were able to deliver comparable prescribing outcomes to doctors. Non-medical prescribers frequently had medical support available to facilitate a collaborative practice model

Verdien av lojalitetsprogram for lojalitet til butikk

Denne oppgaven fokuserer på hvordan verdien av lojalitetsprogram påvirker lojalitet til Coop butikkene. Oppgaven tar for seg de utvalgte individrelaterte faktorene, som funksjonelle, hedonistiske motiver, vane og involvering, for å kunne identifisere hvilke typer kunder som er lojale mot Coop butikkene. Oppgaven undersøker også hvilke av de utvalgte konkurranserelaterte faktorene, som nærhet, pris, personlig interaksjon og væreutvalg, bidrar til lojalitet til Coop butikkene. Til slutt undersøker oppgaven hvilken rolle verdien av Coop sitt lojalitetsprogram spiller for lojalitet til butikk sammenlignet med de individ- og konkurranserelaterte faktorene. Teorien som er brukt i forbindelse med denne oppgaven er hentet fra den generelle begrepsmodellen som forklarer verdien av lojalitetsprogram og butikklojalitet (Liu & Yang, 2009). Vi gjennomførte en kvantitativ spørreskjemaundersøkelse. Utvalget var våre venner og bekjente som besøker Coop butikkene. De statistiske analysene ble gjort ved hjelp av frekvensanalyse, faktoranalyse, reliabilitetsanalyse og hierarkisk og multippel regresjonsanalyse brukt i SPSS

Carbon solving carbon's problems: recent progress of nanostructured carbon-based catalysts for the electrochemical reduction of CO(2)

The electrochemical reduction of CO₂ to useful molecules offers an elegant technological solution to current energy security and sustainability issues because it sequesters carbon from the atmosphere, provides an energy storage solution for intermittent renewable sources, and can be used to produce fuels and industrial chemicals. Nanostructured carbon materials have been extensively used to catalyse some key electrochemical processes because of their excellent electrical conductivity, chemical stability, and abundant active sites. This progress report focuses on nanostructured carbon materials, namely graphene materials, carbon nanotubes, porphyrin materials, nanodiamond, and glassy carbon, which have recently shown promise as high performing CO₂ reduction electrocatalysts and supports. Along with discussion regarding materials synthesis, structural characterisation, and electrochemical performance characterisation techniques used, this report will discuss the findings of recent computational CO₂RR studies which have been key to elucidating active sites and reaction mechanisms, and developing strategies to break conventional scaling relationships. Lastly, challenges and future perspective of these carbon-based materials for CO₂ reduction applications will be given. Much work is still required to realise the commercial viability of the technology, but advanced experimental techniques coupled with theoretical calculations are expected to facilitate future development of the technology.Anthony Vasileff, Yao Zheng, and Shi Zhang Qia