Methylammonium Chloride as a Double-Edged Sword for Efficient and Stable Perovskite Solar Cells.

The additive engineering strategy promotes the efficiency of solution-processed perovskite solar cells (PSCs) over 25%. However, compositional heterogeneity and structural disorders occur in perovskite films with the addition of specific additives, making it imperative to understand the detrimental impact of additives on film quality and device performance. In this work, the double-edged sword effects of the methylammonium chloride (MACl) additive on the properties of methylammonium lead mixed-halide perovskite (MAPbI3-x Clx ) films and PSCs are demonstrated. MAPbI3-x Clx films suffer from undesirable morphology transition during annealing, and its impacts on the film quality including morphology, optical properties, structure, and defect evolution are systematically investigated, as well as the power conversion efficiency (PCE) evolution for related PSCs. The FAX (FA = formamidinium, X = I, Br, and Ac) post-treatment strategy is developed to inhibit the morphology transition and suppress defects by compensating for the loss of the organic components, a champion PCE of 21.49% with an impressive open-circuit voltage of 1.17 V is obtained, and remains over 95% of the initial efficiency after storing over 1200 hours. This study elucidates that understanding the additive-induced detrimental effects in halide perovskites is critical to achieve the efficient and stable PSCs.

Sugarcane-bagasse-ash in enhanced mesophilic Co-digestion for biogas and nutrient recovery: A concept of developing rural circular bioeconomy.

Conductive agro-industrial wastes as accelerants in the anaerobic digestion (AD) of organic waste is a good technique for developing a rural circular economy, such as producing bioenergy and biofertilizer. This study disclosed the a role of sugar cane bagasse ash (SCBA) in enhancing the bioenergy (biogas) yield and digestate fertility via anaerobic co-digestion (AcoD) of buffalo dung (BD) and vegetable residue (VR) under mesophilic conditions (37 á´¼C). Firstly, an optimal BD/VR ratio (1:3) was determined based on biogas yield by introducing five different BD/VR ratios (1:0, 3:1, 1:1, 1:3, and 0:1) into AcoD systems. Secondly, the biogas yield was increased further by adding SCBA at five different concentrations (0, 0.5, 1, 1.5, and 2 wt%). Experimental results disclosed that the 1.5 wt% of SCBA gave the highest cumulative biogas yield (153.67 mL/g VS), COD removal rate (31.18%), and fertility (5.08%). Moreover, a framework is suggested to understand the role of SCBA in the enhanced DIET mechanism. This work documents an environmentally friendly and economical technique for developing a rural circular bioeconomy via the AD of organic agro-waste.

Designing and Understanding the Outstanding Tri-Iodide Reduction of N-Coordinated Magnetic Metal Modified Defect-Rich Carbon Dodecahedrons in Photovoltaics.

Nitrogen-coordinated metal-modified carbon is regarded as a novel frontier electrocatalyst in energy conversion devices. However, the construction of intrinsic defects in a carbon matrix remains a great challenge. Herein, N-coordinated magnetic metal (Fe, Co) modified porous carbon dodecahedrons (Fe/Co-NPCD) with a large surface area, rich intrinsic defects, and evenly distributed metal-Nx species are successfully synthesized via the rational design of iron precursor and the bimetallic-organic frameworks. Because of a synergistic effect between N-coordinated dual magnetic metal active sites, the Fe/Co-NPCD exhibits exceptional electrocatalytic activity and electrochemical stability. A solar cell fabricates with the Fe/Co-NPCD yields an impressive power conversion efficiency of 8.35% in dye-sensitized solar cells, superior to that of mono-metal-doped carbon-based cells and conventional Pt-based cells. Furthermore, density functional theory calculations illustrate that Fe, Co, and N doping are in favor of improving the adsorption capacity of the catalyst for I3 - species by optimizing the magnetic momentum between the magnetic metal atoms, thereby upgrading its catalytic activity. This work develops a general strategy for synthesizing a high-performance defect-rich carbon-based catalyst, and offers valuable insight into the role of magnetic metals in catalysis, which can be used to guide the design of high-performance catalysts in the energy field.

Dye sensitized photoelectrolysis cells.

To advance the progress of photoelectrolysis, various promising devices integrated with p- and n-type photocatalysts and dye sensitized photoelectrodes have been systematically studied. This review discusses, from theory to practice, an integration strategy for state-of-the-art dye sensitized solar cells (DSSCs) with potential p- and n-type photo-electrocatalysts or directly with dye sensitized photoanodes and cathodes for hydrogen and oxygen production through water splitting. Thorough insight into the theoretical approach which systematically drives the photoelectrolysis reaction directly or in a coupled mode, with diverse configurations of DSSCs and other photovoltaic (PV) cells, is crucial to understand the underlying fundamental concepts and elucidate trends in such reactions, and will serve as a guide to design new electrocatalysts and their integration with new PV devices, while simultaneously underlining major gaps that are required to address the challenges. Likewise, challenges, opportunities and frontiers in tandem and hybrid perovskite electrolysis processes are also discoursed in the present tutorial review. We illustrate our analysis by encompassing these integrated systems to photo-electrolysis, artificial photosynthesis such as CO2 conversion into value-added chemical reduction-products, where advancements in new catalysts and solution-processed inexpensive PV devices can certainly enrich the overall performance of the renewable production of solar fuels, including solar driven carbonaceous fuels.

t-Si64 : A Novel Silicon Allotrope.

Utilizing first principle calculations, a novel Si64 silicon allotrope in the I41 /amd space group with tetragonal symmetry (denoted as t-Si64 below) is proposed in this work. In addition, also its structural, anisotropic mechanical, and electronic properties along with its minimum thermal conductivity κmin were predicted. The mechanical and thermodynamic stability of t-Si64 were evaluated by means of elastic constants and phonon spectra. The electronic band structure indicates that t-Si64 is an indirect band gap semiconductor with a band gap: 0.67 eV (primitive cell) compared to a direct band gap of 0.70 eV with respect to a conventional cell. The minimum thermal conductivity of t-Si64 (0.74 W cm-1 K-1 ) is much smaller than that of diamond silicon (1.13 W cm-1 K-1 ). Therefore, Si-Ge alloys in the I41 /amd space group are potential thermoelectric materials.

III-Nitride Polymorphs: XN (X=Al, Ga, In) in the Pnma Phase.

The structural, mechanical, elastic anisotropy, and electronic properties, together with the stability, effective mass of holes and electrons for XN (X=Al, Ga, In) in the Pnma phase are investigated by using density functional theory calculations. The elastic constants and the phonon spectra all manifest III-nitride polymorphs: XN (X=Al, Ga, In) in the Pnma phase in this work are mechanically and dynamically stable at ambient pressure. Al atoms, Ga atoms, and In atoms lead to new electrical and band-gap properties: XN (X=Al, Ga, In) in the Pnma phase are all semiconductor materials with direct band gaps of 4.76 eV, 2.80 eV, and 0.66 eV, respectively, which present great application potentials in the new generation electronic devices such as ultraviolet detectors, visible light detectors, infrared detectors, violet-light diodes, and light-emitting diodes.

Theoretical Treatment of CH3 NH3 PbI3 Perovskite Solar Cells.

Hybrid halide perovskite solar cells (PSCs) giving over 22 % power conversion efficiencies (PCEs) have attracted considerable attention. Although perovskite plays a significant role in the operation of PSCs, the fundamental theories associated with perovskites have not been resolved in spite of the increase in research. In this Minireview, we assess the current understanding, based on the first-principles calculations, of structural and electronic properties, defects, ionic diffusion, and shift current for CH3 NH3 PbI3 perovskite, and the effect of ionic transport on the hysteresis of current-voltage curves in PSCs. The shift current connected to the possible presence of ferroelectricity is also discussed. The current state-of-the-art and some open questions regarding PSCs are also highlighted, and the benefits, challenges, and potentials of perovskite for use in PSCs are stressed.

Quantitative structure-biotransformation relationships of organic micropollutants in aerobic and anaerobic wastewater treatments.

Biotransformation is one of the dominant processes to remove organic micropollutants (OMPs) in wastewater treatment. However, studies on the role of molecular structure in determining the biotransformation rates of OMPs are limited. We evaluated the biotransformation of 14 OMPs belonging to different chemical classes under aerobic and anaerobic conditions, and then explored the quantitative structure-biotransformation relationships (QSBRs) of the OMPs based on biotransformation rates using valid molecular structure descriptors (electrical and physicochemical parameters). Pseudo-first-order kinetic modeling was used to fit the biotransformation rate, and only 2 of the 14 OMPs showed that the biotransformation rate constant (kbio) values were higher under anaerobic conditions than aerobic conditions, indicating that aerobic conditions were more favorable for biotransformation of most OMPs. QSBRs infer that the electrophilicity index (ω) is a reliable predictor for OMPs biotransformation under aerobic conditions. ω corresponds to the interaction between OMPs and microbial enzyme active sites, this process is the rate-limiting step of biotransformation. However, under anaerobic conditions the QSBR based on ω was not significant, indicating that specific functional groups may be more critical than electrophilicity. In conclusion, QSBRs can serve as alternative tools for the prediction of the biotransformation of OMPs and provide further insights into the factors that influence biotransformation.

A new type of low-cost counter electrode catalyst based on platinum nanoparticles loaded onto silicon carbide (Pt/SiC) for dye-sensitized solar cells.

A Pt/SiC nanocomposite with ~10 wt% Pt loading was used as a counter electrode (CE) in dye-sensitized solar cells (DSCs), it shows a high power conversion efficiency (PCE) of 7.07% (a DSC with a SiC CE has a PCE of 3.29%), reaching 98.5% of the level obtained using a Pt CE (7.18%). This work provides substantial support for developing low-cost Pt-loaded composite CEs for DSCs. Pt/SiC use is expected to reduce the dependence on the Pt in DSCs, while it can also be expected to be used in many chemical and electrochemical processes required to control the amount of Pt and prevent Pt nanoparticle aggregation.

Recent progress of crystal orientation engineering in halide perovskite photovoltaics.

Manipulating the crystallographic orientation of semiconductor crystals plays a vital role in fine-tuning their facet-dependent properties, such as surface properties, charge transfer properties, trap state density, and lattice strain. The success in crystal orientation engineering enables the preferential growth orientation of perovskite thin films with favorable crystal planes by precise nucleation manipulation and growth condition optimization, rendering the films with the unique optoelectronic properties to further improve the efficiency of perovskite solar cells (PSCs). However, the origin and impact of preferential crystallographic orientation of perovskite thin films on the corresponding photovoltaic performance of PSCs are still far from being well understood. Herein, we explore the crystal orientation-dependent optoelectronic properties of halide perovskites and their influence on the photovoltaic performance of PSCs. We summarize the basic strategies for crystal facet engineering in the fabrication of preferentially oriented perovskite thin films, with a focus on the oriented growth mechanism during thin film formation. Based on the above knowledge and the recent research progress in terms of crystal orientation engineering in PSCs, a brief outlook on the remaining challenges and perspectives are provided.

Dual utilization of aloe peel: Aloe peel-derived carbon quantum dots enhanced anaerobic co-digestion of aloe peel.

Carbon materials have been widely used in anaerobic digestion (AD), but the role of zero-dimensional carbon quantum dots (CQDs) in anaerobic co-digestion (AcoD) has not yet been reported. In this work, the effect of aloe peel-derived CQDs (AP-CQDs) on the AcoD system of aloe peel and dairy manure was investigated. The addition of AP-CQDs accelerants increased the cumulative CH4 yield from 201.14 to 266.92-339.64 mL/g VS and increased total chemical oxygen demand removal efficiency from 34.72 % to 48.77-57.87 %. The use of a digestate with 0.36 wt.% of AP-CQDs resulted in a thermogravimetric mass loss of 47.15 % and a promising total nutrient content of 46.65 g/kg. The excellent electron exchange capacity of AP-CQDs may facilitate direct interspecies electron transfer during the AD process. Moreover, the use of AP-CQDs can enrich methanogenic microorganisms (Methanosarcina and Methanobacterium). These findings provide a viable strategy for improving methane production and create awareness regarding the dual use of biomass waste.

High-throughput calculation screening for new silicon allotropes with monoclinic symmetry.

A total of 87 new monoclinic silicon allotropes are systematically scanned by a random strategy combined with group and graph theory and high-throughput calculations. The new allotropes include 13 with a direct or quasi-direct band gap and 12 with metallic characteristics, and the rest are indirect band gap semiconductors. More than 30 of these novel monoclinic Si allotropes show bulk moduli greater than or equal to 80 GPa, and three of them show even greater bulk moduli than diamond Si. Only two of the new Si allotropes show a greater shear modulus than diamond Si. The crystal structures, stability (elastic constants, phonon spectra), mechanical properties, electronic properties, effective carrier masses and optical properties of all 87 Si monoclinic allotropes are studied in detail. The electron effective masses ml of five of the new allotropes are smaller than that of diamond Si. All of these novel monoclinic Si allotropes show strong absorption in the visible spectral region. Taken together with their electronic band gap structures, this makes them promising materials for photovoltaic applications. These investigations greatly enrich the current knowledge of the structure and electronic properties of silicon allotropes.

Enhanced methane production in microbial electrolysis cell coupled anaerobic digestion system with MXene accelerants.

Accelerants can improve the anaerobic performance of a microbial electrolysis cell coupled anaerobic digestion (MEC-AD). MAX phase titanium aluminum carbide (MAX), multilayer Ti3C2TX MXene (ML-MXene) and few-layer Ti3C2TX MXene (FL-MXene) were utilized as accelerants for MEC-AD to promote CH4 production and CO2 reduction at a voltage of 0.6 V. The highest CH4 yield (358.7 mL/g VS) and the lowest CO2 yield (57.4 mL/g VS) relative to the control group (170.6 and 125.1 mL/g VS) were obtained in MEC-AD with ML-MXene (0.035 wt%). The digestates of MEC-AD with 0.035 wt% ML-MXene have superior thermal stability (40.9%) and total nutrient content (42.1 g/kg). The ML-MXene enhanced the abundances of Methanosarcina and Methanobacterium. This work highlights the possible role of MXene in promoting methanogenesis. These important findings provide a novel avenue for the development of MXene accelerants for MEC-AD systems.

Designing nitrogen-enriched heterogeneous NiS@CoNi2S4 embedded in nitrogen-doped carbon with hierarchical 2D/3D nanocage structure for efficient alkaline hydrogen evolution and triiodide reduction.

Fabrication of efficient non-precious electrocatalysts with hierarchical nanostructures and the desired compositions is highly desirable to enhance the catalytic activity and stability for hydrogen evolution reaction (HER) and triiodide reduction reaction (IRR). This work proposes a zeolitic imidazolate framework (ZIF) template-based strategy to generate sulfide embedded in nitrogen-doped carbon with a hierarchical 2D/3D nanocage structure. ZIF-67, as a sacrificial template, is first etched to form 2D/3D NiCo layered double hydroxide/2-Methylimidazole (NiCo LDH/MeIm) and then converted to CoNi2S4 nanoparticles embedded in nitrogen-doped carbon (CoNi2S4/NC) through one-step sulfurization and pyrolysis. When a core-shell ZIF-8@ZIF-67 is designed as a template for the generation of Ni@NiCo LDH/MeIm, the obtained NiS@CoNi2S4/NC not only retains the unique 2D/3D nanostructure but also has a high N content, abundant active sites, larger specific surface area, and hierarchical pore distribution. NiS@CoNi2S4/NC mediates an overpotential of 126 mV at 10 mA cm-2 and a Tafel slope of 47.2 mV dec-1 in the alkaline HER. The solar cell equipped with NiS@CoNi2S4/NC as the IRR catalyst achieves a high cell efficiency of 7.96 %. NiS@CoNi2S4/NC shows durably high HER and IRR activity. This controllable synthetic strategy provides a valuable support for developing efficient catalysts in electrocatalytic energy conversion systems.

Mineral residue accelerant-enhanced anaerobic digestion of cow manure: An evaluation system of comprehensive performance.

Anaerobic digestion (AD) is an efficient technology for treating biowaste and generating biogas. A reasonable evaluation of AD performance is crucial to its development. Herein, a comprehensive evaluation system covering five dimensions (energy output, process stability, degradation efficiency, digestate fertility, and digestate safety) was established to assess AD performance. Each dimension in the evaluation system was assigned a specific indicator defined by a threshold or range. Additionally, the proposed evaluation system was applied to assess a case study of batch-mode mesophilic AD that employed three industrial waste residues as mineral accelerants (nickel­iron slag, steel slag, and fly ash). The mineral accelerants enhanced the energy output (methane yield by 66.55 %-87.54 %) and the feedstock degradation (chemical oxygen demand removal ratio by 11.23 %-32.42 %). The digestates also retained promising safety (heavy metal contents of 190-1260 mg/kg) and fertility (total nutrient contents of 3.71 %-4.69 %). The evaluation system reasonably appraised the comprehensive performance of accelerant-enhanced AD systems with cow manure. This work provides a reliable methodology for evaluating and comparing the performance of different novel accelerants and can be applied to evaluate the comprehensive performance of large-scale biogas projects with cow manure.

Niobium- and cobalt-modified dual-source-derived porous carbon with a honeycomb-like stable structure for supercapacitor and hydrogen evolution reaction.

Designing porous carbon materials with tailored architecture and appropriate compositions is essential for supercapacitor (SC) and hydrogen evolution reaction (HER). Herein, Nb/Co-modified dual-source porous carbon (Nb/Co-DSPC) with a honeycomb structure was obtained by introducing a secondary carbon source (Co/Zn-ZIF) and transition metal Nb into activated Typha carbon (ATC). The addition of a secondary carbon source and Nb resulted in superior specific surface area (1272.38 m2/g), excellent hydrophilicity (34.73°) and abundant bimetallic active sites (Nb/Co-Nx) in Nb/Co-DSPC, providing excellent charge storage capacity and electrocatalytic activity. The Nb/Co-DSPC electrode displayed an outstanding capacitance of 337 F/g at 0.5 A/g and showed excellent stability after 15,000 charge-discharge cycles. In addition, Nb/Co-DSPC shows an overpotential of 114 mV at 10 mA cm-2, better than those of Co-DSPC (139 mV) and ATC (162 mV) alone. This study offers a reliable strategy for advanced multifunctional porous carbon electrode materials preparations.

Co-digestion of cow manure and food waste for biogas enhancement and nutrients revival in bio-circular economy.

Anaerobic co-digestion (AcoD) with suitable substrate ratios may have the potential to improve biogas process and could play a better role in nutrient management for biocircular economy. The goal of this study was to enhance biogas yield from AcoD of cow manure (CM) and canteen food waste (CFW), and pertinent co-digestion of suitable substrate ratios for nutrient management i. e NPK from linear to biocircular economy, using ruminant intestinal fluid as a source of inoculum. A mesophilic (37 ± 1 °C) laboratory-scale AcoD with varying CFW/CM ratios of (0:1, 1:4, 2:3, 1:1, 3:2, 4:1, and 1:0) based on wet weight was performed. The AcoD systems of different CFW/CM ratios were evaluated with a loading rate of 400 g/L in the presence of 100 g cow intestinal fluid (CIF) inoculation. All experimental AcoD systems yielded greater biogas (147-300 cm3/g VS) than the mono-digestion in which only CM (135 cm3/g VS) and CFW (146 cm3/g VS) were digested anaerobically. The AcoD system of CFW/CM with 4:1 showed the highest biogas yield (300 cm3/g VS), and VS and COD reduction rate (39.51% and 65.15%, respectively), and nutrient contents (6.53%). Moreover, the experiment results were verified by modified Gompertz model. This work provided a window of opportunity to examine the anaerobic co-digestion technology beyond biogas production and to put the current low-cost technology to use for nutrient management and as a better component of the biocircular economy for agriculture in Pakistan in order to achieve sustainable development goals.

Enhanced methane production in anaerobic co-digestion systems with modified black phosphorus.

Black phosphorus (BP) and BP modified by hydrogen peroxide (MBP) were used as accelerants to enhance CH4 production and CO2 reduction in microbial electrolysis cells (MECs) coupled with anaerobic co-digestion systems (MEC-AcoD). The MEC-AcoD group with a voltage of 0.6 V and 0.03 wt.% of MBP accelerant (MEC0.6MBP0.03) had the largest CH4 yield (242.1 mL/g VS) and the smallest carbon dioxide yield (97.6 mL/g VS) compared with the control group (141.2 mL/g VS, 146.9 mL/g VS). The digestates that used MEC0.6MBP0.03 exhibited superior thermal stability (46.2 %) and total nutrient contents (44.5 g/kg). These improvements may be attributed to the superior electron exchange capacity and physicochemical properties of MBP. Herein, we propose a strategy to understand enhanced CH4 production and CO2 reduction in anaerobic co-digestion and MEC-AcoD systems using MBP accelerants. Notably, combining MBP and MEC could effectively promote anaerobic co-digestion performance.

Mechanism of Potassium Release from Feldspar by Mechanical Activation in Presence of Additives at Ordinary Temperatures.

To improve the potassium availability of feldspar at ordinary temperatures, the mechanical grinding and addition of sodium hydroxide/salts were employed to study the effects of mechanical activation and strong alkali addition on particle characteristics, water-soluble potassium, and the available potassium of feldspar. A laser particle size analyzer was utilized for the direct determination of particle size distribution (PSD) using ground samples. The Brunauer-Emmett-Teller (BET) method was employed for specific surface areas. X-ray diffraction (XRD) was employed for structural characterization, scanning electron microscopy (SEM) for morphology exploration, and energy dispersive spectroscopy (EDS) to determine the chemical composition of potassium feldspar powder. The results revealed that the mechanical activation of potassium feldspar could reduce the particle size and produce agglomerated nanoparticles in the later period. The addition of NaOH and sodium salt did not cause agglomeration, and NaOH dissolved the nanoparticles. The water-soluble potassium content of feldspar in each treatment increased during mechanical grinding, from 21.64 mg kg-1 to 1495.81 mg·kg-1, by adding NaOH 5% weight of potassium feldspar powder and to 3044.08 mg·kg-1 by adding NaOH 10% weight with effects different from those of mechanical shaking. By comparison, only 162.93 mg·kg-1 water-soluble potassium was obtained by adding NaOH 5% weight. The dissolved potassium in the former case was significantly higher than in the latter, and the addition of NaOH and sodium salts significantly enhanced the water-soluble potassium contents due to ion exchange. Furthermore, the addition of sodium hydroxide improved the water-soluble potassium due to its mechanochemical action on potassium feldspar. The mechanical energy changed the crystal structure of potassium feldspar, explaining the increase in available potassium. The addition of sodium salts did not promote change in the feldspar's structure, thereby did not raise the available potassium content. The reason for this was related to the mechanochemical action on sodium hydroxide and feldspar, which could promote the dissolution of fine particles, thereby incrementing the available potassium.

Ni and Fe nanoparticles, alloy and Ni/Fe-Nx coordination co-boost the catalytic activity of the carbon-based catalyst for triiodide reduction and hydrogen evolution reaction.

The design of high-performance early transition metal decorated carbon-based multiple active-site catalysts is of high significance for improving the efficiency of energy utilization. Highly dispersed Fe7Ni3 alloy, Ni and Fe metal nanoparticles and 1D carbon nanotubes (CNTs) decorated metal-nitrogen species (Me-Nx) anchored carbon-based catalysts (Ni NP|Ni-NDC, Fe NP|Fe-NDC, Fe7Ni3|Ni/Fe-NDC) are prepared by a facile in-situ chemical synthesis. As-prepared three nanohybrid catalysts exhibit exceptional catalytic ability and stability for the alkaline hydrogen evolution reaction (HER) and triiodide reduction reaction (IRR). The power conversion efficiency of the dye-sensitized solar cell with the Fe7Ni3|Ni/Fe-NDC counter electrode catalyst reaches 8.58%. The overpotential and corresponding Tafel slope of electrocatalytic water splitting with Fe7Ni3|Ni/Fe-NDC catalyst exhibit 129 mV and 68 mV dec-1 at the current density of 10 mA cm-2 in alkaline solution, respectively. The enhanced catalytic performance of the as-designed hybrid catalysts can be attributed to the synergistic coupling effect of various components (the dispersed Fe7Ni3 alloy, Ni and Fe metal nanoparticles, Ni/Fe-Nx active sites and 1D CNTs) of the hybrid catalyst.