Balancing elementary steps enables coke-free dry reforming of methane.

Balancing kinetics, a crucial priority in catalysis, is frequently achieved by sacrificing activity of elementary steps to suppress side reactions and enhance catalyst stability. Dry reforming of methane (DRM), a process operated at high temperature, usually involves fast C-H activation but sluggish carbon removal, resulting in coke deposition and catalyst deactivation. Studies focused solely on catalyst innovation are insufficient in addressing coke formation efficiently. Herein, we develop coke-free catalysts that balance kinetics of elementary steps for overall thermodynamics optimization. Beginning from a highly active cobalt aluminum oxide (CoAl2O4) catalyst that is susceptible to severe coke formation, we substitute aluminum (Al) with gallium (Ga), reporting a CoAl0.5Ga1.5O4-R catalyst that performs DRM stably over 1000 hours without observable coke deposition. We find that Ga enhances DRM stability by suppressing C-H activation to balance carbon removal. A series of coke-free DRM catalysts are developed herein by partially substituting Al from CoAl2O4 with other metals.

The Lived Experiences of Family Members and Carers of People with Psychosis: A Bottom-Up Review Co-Written by Experts by Experience and Academics.

Informal caregivers of individuals affected by psychotic disorder can play a key role in the recovery process. However, little research has been conducted on the lived experiences of carers and family members. We conducted a bottom-up (from lived experience to theory) review of first-person accounts, co-written between academics and experts by experience, to identify key experiential themes. First-person accounts of carers, relatives, and individuals with psychosis were screened and discussed in collaborative workshops involving individuals with lived experiences of psychosis, family members, and carers, representing various organizations. The lived experiences of family members and carers were characterized by experiential themes related to dealing with the unexpected news, the search for a reason behind the disorder, living with difficult and negative emotions, dealing with loss, feeling lost in fragmented healthcare systems, feeling invisible and wanting to be active partners in care, struggling to communicate with the affected person, fighting stigma and isolation, dealing with an uncertain future, and learning from one's mistakes and building resilience and hope. Our findings bring forth the voices of relatives and informal carers of people with psychosis, by highlighting some of the common themes of their lived experiences from the time of the initial diagnosis and throughout the different clinical stages of the disorder. Informal carers are key stakeholders who can play a strategic role, and their contributions in the recovery process merit recognition and active support by mental health professionals.

Determination of a Raman shift laser power coefficient based on cross correlation.

This work presents a novel, to the best of our knowledge, cross correlation technique for determining the laser heating-induced Raman shift laser power coefficient ψ required for energy transport state-resolved Raman (ET-Raman) methods. The cross correlation method determines the measure of similarity between the experimental intensity data and a varying test Gaussian signal. By circumventing the errors inherent in any curve fittings, the cross correlation method quickly and accurately determines the location where the test Gaussian signal peak is most like the Raman peak, thereby revealing the peak location and ultimately the value of ψ. This method improves the reliability of optothermal Raman-based methods for micro/nanoscale thermal measurements and offers a robust approach to data processing through a global treatment of Raman spectra.

Critical problems faced in Raman-based energy transport characterization of nanomaterials.

In the last two decades, tremendous research has been conducted on the discovery, design and synthesis, characterization, and applications of two-dimensional (2D) materials. Thermal conductivity and interface thermal conductance/resistance of 2D materials are two critical properties in their applications. Raman spectroscopy, which measures the inelastic scattering of photons by optical phonons, can distinct a 2D material's temperature from its surrounding materials', featuring unprecedented spatial resolution (down to the atomic level). Raman-based thermometry has been used tremendously for characterizing the thermal conductivity of 2D materials (suspended or supported) and interface thermal conductance/resistance. Very large data deviations have been observed in literature, partly due to physical phenomena and factors not considered in measurements. Here, we provide a critical review, analysis, and perspectives about a broad spectrum of physical problems faced in Raman-based thermal characterization of 2D materials, namely interface separation, localized stress due to thermal expansion mismatch, optical interference, conjugated phonon, and hot carrier transport, optical-acoustic phonon thermal nonequilibrium, and radiative electron-hole recombination in monolayer 2D materials. Neglect of these problems will lead to a physically unreasonable understanding of phonon transport and interface energy coupling. In-depth discussions are also provided on the energy transport state-resolved Raman (ET-Raman) technique to overcome these problems and on future research challenges and needs.

Laser Photoreduction of Graphene Aerogel Microfibers: Dynamic Electrical and Thermal Behaviors.

This work reports the dynamic behaviors of graphene aerogel (GA) microfibers during and after continuous wave (CW) laser photoreduction. The reduction results in one-order of magnitude increase in the electrical conductivity. The experimental results reveal the exact mechanisms of photoreduction as it occurs: immediate photochemical removal of oxygen functional groups causing a sharp decrease in electrical resistance and subsequent laser heating that facilitates thermal rearrangement of GO sheets towards more graphene-like domains. X-ray and Raman spectroscopy analysis confirm that photoreduction removes virtually all oxygen and nitrogen containing functional groups. Interestingly, a dynamic period immediately following the end of laser exposure shows a slow, gradual increase in electrical resistance, suggesting that a proportion of the electrical conductivity enhancement from photoreduction is not permanent. A two-part experiment monitoring the resistance changes in real-time before and after photoreduction is conducted to investigate this critical period. The thermal diffusivity evolution of the microfiber is tracked and shows an improvement of 277 % after all photoreduction experiments. A strong linear coherency between thermal diffusivity and electrical conductivity is also uncovered. This is the first known work to explore both the dynamic electrical and thermal evolution of a GO-based aerogel during and after photoreduction.

The lived experience of psychosis: a bottom-up review co-written by experts by experience and academics.

Psychosis is the most ineffable experience of mental disorder. We provide here the first co-written bottom-up review of the lived experience of psychosis, whereby experts by experience primarily selected the subjective themes, that were subsequently enriched by phenomenologically-informed perspectives. First-person accounts within and outside the medical field were screened and discussed in collaborative workshops involving numerous individuals with lived experience of psychosis as well as family members and carers, representing a global network of organizations. The material was complemented by semantic analyses and shared across all collaborators in a cloud-based system. The early phases of psychosis (i.e., premorbid and prodromal stages) were found to be characterized by core existential themes including loss of common sense, perplexity and lack of immersion in the world with compromised vital contact with reality, heightened salience and a feeling that something important is about to happen, perturbation of the sense of self, and need to hide the tumultuous inner experiences. The first episode stage was found to be denoted by some transitory relief associated with the onset of delusions, intense self-referentiality and permeated self-world boundaries, tumultuous internal noise, and dissolution of the sense of self with social withdrawal. Core lived experiences of the later stages (i.e., relapsing and chronic) involved grieving personal losses, feeling split, and struggling to accept the constant inner chaos, the new self, the diagnosis and an uncertain future. The experience of receiving psychiatric treatments, such as inpatient and outpatient care, social interventions, psychological treatments and medications, included both positive and negative aspects, and was determined by the hope of achieving recovery, understood as an enduring journey of reconstructing the sense of personhood and re-establishing the lost bonds with others towards meaningful goals. These findings can inform clinical practice, research and education. Psychosis is one of the most painful and upsetting existential experiences, so dizzyingly alien to our usual patterns of life and so unspeakably enigmatic and human.

Direct Characterization of Thermal Nonequilibrium between Optical and Acoustic Phonons in Graphene Paper under Photon Excitation.

Raman spectroscopy has been widely used to measure thermophysical properties of 2D materials. The local intense photon heating induces strong thermal nonequilibrium between optical and acoustic phonons. Both first principle calculations and recent indirect Raman measurements prove this phenomenon. To date, no direct measurement of the thermal nonequilibrium between optical and acoustic phonons has been reported. Here, this physical phenomenon is directly characterized for the first time through a novel approach combining both electrothermal and optothermal techniques. While the optical phonon temperature is determined from Raman wavenumber, the acoustic phonon temperature is precisely determined using high-precision thermal conductivity and laser power absorption that are measured with negligible nonequilibrium among energy carriers. For graphene paper, the energy coupling factor between in-plane optical and overall acoustic phonons is found at (1.59-3.10) × 1015 W m-3 K-1, agreeing well with the quantum mechanical modeling result of 4.1 × 1015 W m-3 K-1. Under ≈1 µm diameter laser heating, the optical phonon temperature rise is over 80% higher than that of the acoustic phonons. This observation points out the importance of subtracting optical-acoustic phonon thermal nonequilibrium in Raman-based thermal characterization.

Pastoral Care in Aged Care Settings: Role and Challenges.

This mixed methods study explored challenges faced by pastoral care workers. A development phase preceded an on-line survey completed by chaplains and pastoral practitioners (n = 40) employed by a major Australian aged care provider. The survey covered the purpose of pastoral care, key tasks and resources, current and future challenges, and participants' responses to challenges. The biggest issue was heavy demand on participants' time, due to insufficient staff and demanding organisational procedures. A commonly mentioned challenge with future implications was increasing resident acuity. Respondents were dedicated and enthusiastic, despite heavy workloads and occasional difficulty working with care staff or management.

Interfacial Thermal Conductance between Monolayer WSe2 and SiO2 under Consideration of Radiative Electron-Hole Recombination.

This work reports the interfacial thermal conductance (G) and radiative recombination efficiency (ß), also known as photoluminescence quantum yield (PL QY), of monolayer WSe2 flakes supported by fused silica substrates via energy-transport state-resolved Raman (ET-Raman). This is the first known work to consider the effect of radiative electron-hole recombination on the thermal transport characteristics of single-layer transition-metal dichalcogenides (TMDs). ET-Raman uses a continuous-wave laser for steady-state heating as well as nanosecond and picosecond lasers for transient energy transport to simultaneously heat the monolayer flakes and extract the Raman signal. The three lasers induce distinct heating phenomena that distinguish the interfacial thermal conductance and radiative recombination efficiency, which can then be determined in tandem with three-dimensional (3D) numerical modeling of the temperature rise from respective laser irradiation. For the five samples measured, G is found to range from 2.10 ± 0.14 to 15.9 ± 5.0 MW m-2 K-1 and ß ranges from 36 ± 6 to 65 ± 7%. These values support the claim that interfacial phenomena such as surface roughness and two-dimensional (2D) material-substrate bonding strength play critical roles in interfacial thermal transport and electron-hole recombination mechanisms in TMD monolayers. It is also determined that low-level defect density enhances the radiative recombination efficiency of single-layer WSe2.

Thermal conductance between water and nm-thick WS2: extremely localized probing using nanosecond energy transport state-resolved Raman.

Liquid-solid interface energy transport has been a long-term research topic. Past research mostly focused on theoretical studies while there are only a handful of experimental reports because of the extreme challenges faced in measuring such interfaces. Here, by constructing nanosecond energy transport state-resolved Raman spectroscopy (nET-Raman), we characterize thermal conductance across a liquid-solid interface: water-WS2 nm film. In the studied system, one side of a nm-thick WS2 film is in contact with water and the other side is isolated. WS2 samples are irradiated with 532 nm wavelength lasers and their temperature evolution is monitored by tracking the Raman shift variation in the E2g mode at several laser powers. Steady and transient heating states are created using continuous wave and nanosecond pulsed lasers, respectively. We find that the thermal conductance between water and WS2 is in the range of 2.5-11.8 MW m-2 K-1 for three measured samples (22, 33, and 88 nm thick). This is in agreement with molecular dynamics simulation results and previous experimental work. The slight differences are attributed mostly to the solid-liquid interaction at the boundary and the surface energies of different solid materials. Our detailed analysis confirms that nET-Raman is very robust in characterizing such interface thermal conductance. It completely eliminates the need for laser power absorption and Raman temperature coefficients, and is insensitive to the large uncertainties in 2D material properties input.