Nanometer-Resolved Operando Photo-Response of Faceted BiVO4 Semiconductor Nanoparticles.

Photo(electro)catalysis with semiconducting nanoparticles (NPs) is an attractive approach to convert abundant but intermittent renewable electricity into stable chemical fuels. However, our understanding of the microscopic processes governing the performance of the materials has been hampered by the lack of operando characterization techniques with sufficient lateral resolution. Here, we demonstrate that the local surface potentials of NPs of bismuth vanadate (BiVO4) and their response to illumination differ between adjacent facets and depend strongly on the pH of the ambient electrolyte. The isoelectric points of the dominant {010} basal plane and the adjacent {110} side facets differ by 1.5 pH units. Upon illumination, both facets accumulate positive charges and display a maximum surface photoresponse of +55 mV, much stronger than reported in the literature for the surface photo voltage of BiVO4 NPs in air. High resolution images reveal the presence of numerous surface defects ranging from vacancies of a few atoms, to single unit cell steps, to microfacets of variable orientation and degree of disorder. These defects typically carry a highly localized negative surface charge density and display an opposite photoresponse compared to the adjacent facets. Strategies to model and optimize the performance of photocatalyst NPs, therefore, require an understanding of the distribution of surface defects, including the interaction with ambient electrolyte.

Photophysical Study on the Effect of the External Potential on NiO-Based Photocathodes.

In the present study, we investigate the effects of the applied external potential on a dye-sensitized NiO photocathode by time-resolved photoluminescence and femtosecond transient absorption spectroscopy under operating conditions. Instead of the anticipated acceleration of photoinduced hole injection from dye into NiO at a more negative applied potential, we observe that both hole injection and charge recombination are slowed down. We cautiously assign this effect to a variation in OH- ion concentration in the inner Helmholtz plane of the electrochemical double layer with applied potential, warranting further investigation for the realization of efficient solar fuel devices.

CuBO2 : A Potential Alternative for NiO as a Hole Acceptor Layer.

P-type metal oxides, and in particular NiO, are typically used as hole accepting layers in dye-sensitized photocathodes. Delafossites (CuMO2 ) with M=B, Al, Cr or Ga have recently been proposed as attractive substitutes for NiO, with theoretically a higher hole mobility than NiO, therefore allowing a higher efficiency when the photocathode is applied in solar to fuel devices. We have experimentally validated the photoelectrochemical performance of photocathodes consisting of nanoporous CuBO2 (CBO) on Fluorine-doped Tin Oxide substrates, photosensitized with a light absorbing P1 dye. Femtosecond transient absorption and time-resolved photoluminescence studies show that light-induced hole injection occurs from the P1 dye into the CBO in a few ps, comparable to the time constant observed for NiO-based photocathodes. Importantly, the CBO-based photocathode shows significantly slower charge recombination than the NiO-based analogue. These results illustrate the promise of CBO as a p-type semiconductor in solar energy conversion devices.

Disentangling Hot Carrier Decay and the Nature of Low-n to High-n Transfer Processes in Quasi-Two-Dimensional Layered Perovskites.

Quasi-two-dimensional (2D) metal halide perovskites (MHPs) are promising photovoltaic (PV) materials because of their impressive optical and optoelectronic properties and improved stability compared to their 3D counterparts. The presence of domains with varying numbers of inorganic layers between the organic spacers (n-phases), each with different bandgaps, makes the photoinduced carrier dynamics in films of these materials complex and intriguing. Existing interpretations of the ultrafast femto- or picosecond spectroscopy data have been inconsistent, most of them focusing either on exciton/charge transfer from low-n to high-n phases or on hot carrier cooling, but not combined. Here, we present a comprehensive study of the carrier dynamics in the Dion-Jacobson type (PDMA)(MA)(n-1)PbnI(3n+1) (PDMA = 1,4-phenylenedimethylammonium, MA = methylammonium) perovskite, stoichiometrically prepared as ⟨n⟩ = 5. Within the film, a coexistence of various n-phases is observed instead of solely the n = 5 phase, resulting in an interesting energy landscape for the motion of excitons and charge carriers. We disentangle hot carrier cooling from exciton transfer between low-n and high-n phases using ultrafast time-resolved photoluminescence and transient absorption spectroscopy. Photophysical modeling by target analysis shows that carrier cooling occurring on a subpicosecond time scale is followed by exciton transfer from low-n into high-n phases in ca. 35 ps when the film is excited by 532 or 490 nm light. Carriers in the high-n phase are much longer lived and decay in a ns time window. Overall, our results provide a comprehensive understanding of the photophysics of this material, which helps to optimize quasi-2D MHP materials for a new generation of PV devices.

Photon Energy-Dependent Ultrafast Exciton Transfer in Chlorosomes of Chlorobium tepidum and the Role of Supramolecular Dynamics.

The antenna complex of green sulfur bacteria, the chlorosome, is one of the most efficient supramolecular systems for efficient long-range exciton transfer in nature. Femtosecond transient absorption experiments provide new insight into how vibrationally induced quantum overlap between exciton states supports highly efficient long-range exciton transfer in the chlorosome of Chlorobium tepidum. Our work shows that excitation energy is delocalized over the chlorosome in <1 ps at room temperature. The following exciton transfer to the baseplate occurs in ∼3 to 5 ps, in line with earlier work also performed at room temperature, but significantly faster than at the cryogenic temperatures used in previous studies. This difference can be attributed to the increased vibrational motion at room temperature. We observe a so far unknown impact of the excitation photon energy on the efficiency of this process. This dependency can be assigned to distinct optical domains due to structural disorder, combined with an exciton trapping channel competing with exciton transfer toward the baseplate. An oscillatory transient signal damped in <1 ps has the highest intensity in the case of the most efficient exciton transfer to the baseplate. These results agree well with an earlier computational finding of exciton transfer driven by low-frequency rotational motion of molecules in the chlorosome. Such an exciton transfer process belongs to the quantum coherent regime, for which the Förster theory for intermolecular exciton transfer does not apply. Our work hence strongly indicates that structural flexibility is important for efficient long-range exciton transfer in chlorosomes.

Photophysical Characterization of Ru Nanoclusters on Nanostructured TiO2 by Time-Resolved Photoluminescence Spectroscopy.

Despite the promising performance of Ru nanoparticles or nanoclusters on nanostructured TiO2 in photocatalytic and photothermal reactions, a mechanistic understanding of the photophysics is limited. The aim of this study is to uncover the nature of light-induced processes in Ru/TiO2 and the role of UV versus visible excitation by time-resolved photoluminescence (PL) spectroscopy. The PL at a 267 nm excitation is predominantly due to TiO2, with a minor contribution of the Ru nanoclusters. Relative to TiO2, the PL of Ru/TiO2 following a 267 nm excitation is significantly blue-shifted, and the bathochromic shift with time is smaller. We show by global analysis of the spectrotemporal PL behavior that for both TiO2 and Ru/TiO2 the bathochromic shift with time is likely caused by the diffusion of electrons from the TiO2 bulk toward the surface. During this directional motion, electrons may recombine (non)radiatively with relatively immobile hole polarons, causing the PL spectrum to red-shift with time following excitation. The blue-shifted PL spectra and smaller bathochromic shift with time for Ru/TiO2 relative to TiO2 indicate surface PL quenching, likely due to charge transfer from the TiO2 surface into the Ru nanoclusters. When deposited on SiO2 and excited at 532 nm, Ru shows a strong emission. The PL of Ru when deposited on TiO2 is completely quenched, demonstrating interfacial charge separation following photoexcitation of the Ru nanoclusters with a close to unity quantum yield. The nature of the charge-transfer phenomena is discussed, and the obtained insights indicate that Ru nanoclusters should be deposited on semiconducting supports to enable highly effective photo(thermal)catalysis.

Electrochemical decarboxylation of acetic acid on boron-doped diamond and platinum-functionalised electrodes for pyrolysis-oil treatment.

Electrochemical decarboxylation of acetic acid on boron-doped-diamond (BDD) electrodes was studied as a possible means to decrease the acidity of pyrolysis oil. It is shown that decarboxylation occurs without the competitive oxygen evolution reaction (OER) on BDD electrodes to form methanol and methyl acetate by consecutive reaction of hydroxyl radicals with acetic acid. The performance is little affected by the applied current density (and associated potential), concentration, and the pH of the solution. At current densities above 50 mA cm-2, faradaic efficiencies (FEs) of 90% towards the decarboxylation products are obtained, confirmed by in situ electrochemical mass spectrometry (ECMS) investigation showing only small amounts of oxygen formed by water oxidation. Using platinum-modified BDD electrodes, it is shown that selectivity to ethane, the Kolbe product, strongly depends on the shape and geometry of the platinum particles. Using nano-thorn-like Pt particles, a faradaic efficiency of approx. 40% towards ethane can be obtained, whereas 3D porous platinum nanoparticles showed high selectivity towards the OER. Using thin platinum layers, a high FE of >70% towards ethane was obtained, which is thickness-independent at layer thicknesses above 20 nm. Comparison with other substrates revealed that BDD is an ideal support for Pt functionalisation, giving advantages of stability and high-value-product formation (ethane and methanol). In short, this work provides guidelines for electrode fabrication in the context of the electrochemical upgrading of biomass feedstocks by acid decarboxylation.

What It Takes for Imidazolium Cations to Promote Electrochemical Reduction of CO2.

Imidazolium cations enhance the performance of several electrodes in converting CO2 to CO in non-aqueous media. In this publication, we elucidate the origin of the function of imidazolium cations when exposed to Au electrodes in anhydrous acetonitrile in CO2 atmosphere. We demonstrate that imidazolium cations lead to unprecedentedly low overpotentials for CO2 reduction to CO on Au, with ∼100% Faradaic efficiency. By modification of the N1 and N3 functionality of the imidazolium cation, we show a direct correlation between the performance in CO2 reduction and the C2-H acidity of the cation. Based on NMR analyses, DFT calculations, and isotopic labeling, showing an inverse kinetic isotope effect, we demonstrate that the mechanism involves a concerted proton-electron transfer to the electrode-adsorbed CO2 intermediate. The demonstrated mechanism provides guidelines for improvement in the energy efficiency of non-aqueous electrochemical CO2 reduction, by a tailored design of electrolyte cations.

Dual Role of Surface Hydroxyl Groups in the Photodynamics and Performance of NiO-Based Photocathodes.

Photoelectrochemical (PEC) cells containing photocathodes based on functionalized NiO show a promising solar-to-hydrogen conversion efficiency. Here, we present mechanistic understanding of the photoinduced charge transfer processes occurring at the photocathode/electrolyte interface. We demonstrate via advanced photophysical characterization that surface hydroxyl groups formed at the NiO/water interface not only promote photoinduced hole transfer from the dye into NiO, but also enhance the rate of charge recombination. Both processes are significantly slower when the photocathode is exposed to dry acetonitrile, while in air an intermediate behavior is observed. These data suggest that highly efficient devices can be developed by balancing the quantity of surface hydroxyl groups of NiO, and presumably of other p-type metal oxide semiconductors.

Facet-Dependent Surface Charge and Hydration of Semiconducting Nanoparticles at Variable pH.

Understanding structure and function of solid-liquid interfaces is essential for the development of nanomaterials for various applications including heterogeneous catalysis in liquid phase processes and water splitting for storage of renewable electricity. The characteristic anisotropy of crystalline nanoparticles is believed to be essential for their performance but remains poorly understood and difficult to characterize. Dual scale atomic force microscopy is used to measure electrostatic and hydration forces of faceted semiconducting SrTiO3 nanoparticles in aqueous electrolyte at variable pH. The following are demonstrated: the ability to quantify strongly facet-dependent surface charges yielding isoelectric points of the dominant {100} and {110} facets that differ by as much as 2 pH units; facet-dependent accumulation of oppositely charged (SiO2 ) particles; and that atomic scale defects can be resolved but are in fact rare for the samples investigated. Atomically resolved images and facet-dependent oscillatory hydration forces suggest a microscopic charge generation mechanism that explains colloidal scale electrostatic forces.

Unraveling the Mechanisms of Beneficial Cu-Doping of NiO-Based Photocathodes.

Dye-sensitized photoelectrochemical (DSPEC) water splitting is an attractive approach to convert and store solar energy into chemical bonds. However, the solar conversion efficiency of a DSPEC cell is typically low due to a poor performance of the photocathode. Here, we demonstrate that Cu-doping improves the performance of a functionalized NiO-based photocathode significantly. Femtosecond transient absorption experiments show longer-lived photoinduced charge separation for the Cu:NiO-based photocathode relative to the undoped analogue. We present a photophysical model that distinguishes between surface and bulk charge recombination, with the first process (∼10 ps) occurring more than 1 order of magnitude faster than the latter. The longer-lived photoinduced charge separation in the Cu:NiO-based photocathode likely originates from less dominant surface recombination and an increased probability for holes to escape into the bulk and to be transported to the electrical contact of the photocathode. Cu-doping of NiO shows promise to suppress detrimental surface charge recombination and to realize more efficient photocathodes.

CrOx-Mediated Performance Enhancement of Ni/NiO-Mg:SrTiO3 in Photocatalytic Water Splitting.

By photodeposition of CrOx on SrTiO3-based semiconductors doped with aliovalent Mg(II) and functionalized with Ni/NiOx catalytic nanoparticles (economically significantly more viable than commonly used Rh catalysts), an increase in apparent quantum yield (AQYs) from ∼10 to 26% in overall water splitting was obtained. More importantly, deposition of CrOx also significantly enhances the stability of Ni/NiO nanoparticles in the production of hydrogen, allowing sustained operation, even in intermittent cycles of illumination. In situ elemental analysis of the water constituents during or after photocatalysis by inductively coupled plasma mass spectrometry/optical emission spectrometry shows that after CrOx deposition, dissolution of Ni ions from Ni/NiOx-Mg:SrTiO3 is significantly suppressed, in agreement with the stabilizing effect observed, when both Mg dopant and CrOx are present. State-of-the-art electron microscopy and energy-dispersive X-ray spectroscopy (EDX) and electron energy-loss spectroscopy (EELS) analyses demonstrate that upon preparation, CrOx is photodeposited in the vicinity of several, but not all, Ni/NiOx particles. This implies the formation of a Ni-Cr mixed metal oxide, which is highly effective in water reduction. Inhomogeneities in the interfacial contact, evident from differences in contact angles between Ni/NiOx particles and the Mg:SrTiO3 semiconductor, likely affect the probability of reduction of Cr(VI) species during synthesis by photodeposition, explaining the observed inhomogeneity in the spatial CrOx distribution. Furthermore, by comparison with undoped SrTiO3, Mg-doping appears essential to provide such favorable interfacial contact and to establish the beneficial effect of CrOx. This study suggests that the performance of semiconductors can be significantly improved if inhomogeneities in interfacial contact between semiconductors and highly effective catalytic nanoparticles can be resolved by (surface) doping and improved synthesis protocols.

Synergy of ferroelectric polarization and oxygen vacancy to promote CO2 photoreduction.

Solar-light driven CO2 reduction into value-added chemicals and fuels emerges as a significant approach for CO2 conversion. However, inefficient electron-hole separation and the complex multi-electrons transfer processes hamper the efficiency of CO2 photoreduction. Herein, we prepare ferroelectric Bi3TiNbO9 nanosheets and employ corona poling to strengthen their ferroelectric polarization to facilitate the bulk charge separation within Bi3TiNbO9 nanosheets. Furthermore, surface oxygen vacancies are introduced to extend the photo-absorption of the synthesized materials and also to promote the adsorption and activation of CO2 molecules on the catalysts' surface. More importantly, the oxygen vacancies exert a pinning effect on ferroelectric domains that enables Bi3TiNbO9 nanosheets to maintain superb ferroelectric polarization, tackling above-mentioned key challenges in photocatalytic CO2 reduction. This work highlights the importance of ferroelectric properties and controlled surface defect engineering, and emphasizes the key roles of tuning bulk and surface properties in enhancing the CO2 photoreduction performance.

Optimizing CO Coverage on Rough Copper Electrodes: Effect of the Partial Pressure of CO and Electrolyte Anions (pH) on Selectivity toward Ethylene.

The conversion of the initial intermediate CO in the electrochemical reduction reaction of CO2 on the surface of oxide-derived Cu electrodes has been investigated as a function of partial pressure and pH, manipulated by the composition of the electrolyte. We show that in inert gas, an increase in partial pressure of CO results in a continuous increase in Faradaic efficiency (FE) for ethylene, at various potentials ranging from -0.7 to -1.1 V versus RHE, with the highest FE of ∼28% obtained using 1 bar CO at -0.8 V. When the partial pressure of CO is increased in a mixture of CO and CO2, an optimum in the ethylene FE was found for the partial pressure of CO in the range from 0.5 bar (at -1.1 V, FE is ∼45%) to 0.8 bar (at -0.9 V, FE is ∼35%). At lower negative potentials (-0.8 to -0.7 V), the presence of CO2 has negligible influence, and similar data to reduction of CO in inert gas were obtained. Variation of the anion in solution (0.1 M concentration) shows that the optimized FE toward ethylene increases from 5.2% in KH2PO4 to 43.2% in KOH. The observed differences in selectivity are attributed to anion buffering capacity and the associated local pH near the surface of the electrode. Using in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), it was determined that the CO coverage increases as a function of increasing pH, confirming that CO coverage and pH correlate. Collectively, the data herein outline the critical role of reactant partial pressures and the significant effect of anion composition (pH) on the surface coverage of CO and concomitant selectivity in electrochemical reduction of CO2 to ethylene.

Modular microreactor with integrated reflection element for online reaction monitoring using infrared spectroscopy.

We report on the fabrication of an internal reflection element (IRE) combined with a modular polymer microfluidic chip that can be used for attenuated total reflection (ATR) infrared spectroscopy. The IRE is fabricated from a silicon wafer. Two different polymers are used for the fabrication of the two types of modular microfluidic chips, namely polydimethylsiloxane (PDMS) and cyclic olefin copolymer (COC). The microfluidic chip is modular in the sense that several layers of mixing channels, using the herringbone mixer principle, and reactions chambers, can be stacked to facilitate the study of the desired reaction. A model Paal-Knorr reaction is carried out to prove that the chip works as intended. Furthermore, we highlight the strength of IR spectroscopy as a tool for reaction monitoring by identifying the peaks and showing the different reaction orders at the different steps of the Paal-Knorr reaction. The reduction of the aldehyde groups indicates a (pseudo) first order reaction whereas the vibrational modes associated with the ring formation indicate a zero order reaction. This zero order reaction can be explained with literature, where it is suggested that water acts as a catalyst during the dehydration step, which is the final step in the pyrrole ring formation.

Electrochemically Induced pH Change: Time-Resolved Confocal Fluorescence Microscopy Measurements and Comparison with Numerical Model.

Confocal fluorescence microscopy is a proven technique, which can image near-electrode pH changes. For a complete understanding of electrode processes, time-resolved measurements are required, which have not been achieved previously. Here we present the first measurements of time-resolved pH profiles with confocal fluorescence microscopy. The experimental results compare favorably with a one-dimensional reaction-diffusion model; this holds up to the point where the measurements reveal three-dimensionality in the pH distribution. Specific factors affecting the pH measurement such as attenuation of light and the role of dye migration are also discussed in detail. The method is further applied to reveal the buffer effects observed in sulfate-containing electrolytes. The work presented here is paving the way toward the use of confocal fluorescence microscopy in the measurement of 3D time-resolved pH changes in numerous electrochemical settings, for example, in the vicinity of bubbles.

Photocatalytic Oxidation of Propane Using Hydrothermally Prepared Anatase-Brookite-Rutile TiO2 Samples. An In Situ DRIFTS Study.

Photocatalytic oxidation of propane using hydrothermally synthesized TiO2 samples with similar primary crystal size containing different ratios of anatase, brookite and rutile phases has been studied by measuring light-induced propane conversion and in situ DRIFTS (diffuse reflectance Fourier transform infrared spectroscopy). Propane was found to adsorb on the photocatalysts, both in the absence and presence of light. The extent of adsorption depends on the phase composition of synthesized titania powders and, in general, it decreases with increasing rutile and brookite content. Still, the intrinsic activity for photocatalytic decomposition of propane is higher for photocatalysts with lower ability for propane adsorption, suggesting this is not the rate-limiting step. In situ DRIFTS analysis shows that bands related to adsorbed acetone, formate and bicarbonate species appear on the surface of the photocatalysts during illumination. Correlation of propane conversion and infrared (IR) data shows that the presence of formate and bicarbonate species, in excess with respect to acetone, is composition dependent, and results in relatively low activity of the respective TiO2. This study highlights the need for precise control of the phase composition to optimize rates in the photocatalytic oxidation of propane and a high rutile content seems to be favorable.

Preparation of Ti, Ti/TiC or Ti/TiN based hollow fibres with extremely low electrical resistivity.

Porous Ti based hollow fibres with extremely low electrical resistivity (4.1-9.6 µΩ m), orders of magnitude smaller than reported for Ti-fibres in the literature, were produced by dry-wet spinning of a mixture of Ti-particles, polyethersulfone (PES), and N-methylpyrrolidone (NMP). Utilizing a two-step thermal decomposition of PES, consisting of treatment in air at 475 °C, followed by treatment in argon at 800 °C, hollow fibres of entirely metallic Ti are obtained, as confirmed by XRD, SEM-EDS, and TGA-MS analyses. Only a thin oxide layer is formed due to ambient surface oxidation, as identified by XPS analysis. Carbonization of the polymer under an inert atmosphere can be used to produce a Ti/TiC-composite. To obtain a Ti/TiN composite, the porous Ti-tubes can be treated in nitrogen atmosphere at 800 °C. The porosity, pore size distribution, and bending-strength of the fibres were determined for a low (800 °C) and high (1100 °C) degree of sintering, and it was found that these are largely independent of the chemical surface composition. The presence of TiC or TiN, likely in an outer, but crystalline shell (based on XRD and XPS data), results in lower resistivity than of the pure Ti fibres, which can be attributed to the insulating layer of TiC or TiN preventing capacitive effects at the Ti/air interface. The developed preparation methodology results in porous metallic and composite Ti based fibres, which are very suitable for electrochemical applications.

Silver Nanocubes Coated in Ceria: Core/Shell Size Effects on Light-Induced Charge Transfer.

Plasmonic sensitization of semiconductors is an attractive approach to increase light-induced photocatalytic performance; one method is to use plasmonic nanostructures in core@shell geometry. The occurrence and mechanism of synergetic effects in photocatalysis of such geometries are under intense debate and proposed to occur either through light-induced charge transfer (CT) or through thermal effects. This study focuses on the relation between the dimensions of Ag@CeO2 nanocubes, the wavelength-dependent efficiency, and the mechanism of light-induced direct CT. A 4-mercaptobenzoic acid (4-MBA) linker between core and shell acts as a Raman probe for CT. For all Ag@CeO2 nanocubes, CT increases with decreasing excitation wavelength, with notable increase at and below 514 nm. This is fully explainable by CT from silver to the 4-MBA LUMO, with the increase for excitation wavelengths that exceed the Ag/4-MBA LUMO gap of 2.28 eV (543 nm). A second general trend observed is an increase in CT yield with ceria shell thickness, which is assigned to relaxation of the excited electron further into the ceria conduction band, potentially producing defects.

Comparative Analysis of Photocatalytic and Electrochemical Degradation of 4-Ethylphenol in Saline Conditions.

We evaluated electrochemical degradation (ECD) and photocatalytic degradation (PCD) technologies for saline water purification, with a focus on rate comparison and formation and degradation of chlorinated aromatic intermediates using the same non-chlorinated parent compound, 4-ethylphenol (4EP). At 15 mA·cm-2, and in the absence of chloride (0.6 mol·L-1 NaNO3 was used as supporting electrolyte), ECD resulted in an apparent zero-order rate of 30 µmol L-1·h-1, whereas rates of ∼300 µmol L-1·h-1 and ∼3750 µmol L-1·h-1 were computed for low (0.03 mol·L-1) and high (0.6 mol·L-1) NaCl concentration, respectively. For PCD, initial rates of ∼330 µmol L-1·h-1 and 205 µmol L-1·h-1 were found for low and high NaCl concentrations, at a photocatalyst (TiO2) concentration of 0.5 g·L-1, and illumination at λmax ≈ 375 nm, with an intensity ∼0.32 mW·cm-2. In the chlorine mediated ECD approach, significant quantities of free chlorine (hypochlorite, Cl2) and chlorinated hydrocarbons were formed in solution, while photocatalytic degradation did not show the formation of free chlorine, nor chlorine-containing intermediates, and resulted in better removal of non-purgeable hydrocarbons than ECD. The origin of the minimal formation of free chlorine and chlorinated compounds in photocatalytic degradation is discussed based on photoelectrochemical results and existing literature, and explained by a chloride-mediated surface-charge recombination mechanism.