Charge Compensation Research Articles

Near-Infrared Persistent Luminescence of CaTiO3:Cr,Y for Imaging of Bone Implants Using Red-Light Illumination Instead of X-ray.

Near-infrared (NIR) persistent luminescence (PersL) materials have unique optical properties with promising applications in bioimaging and anticounterfeiting. However, their development is currently hindered by poor red-light-exciting ability. In this study, CaTiO3:Cr0.001,Y0.02 (CTCY) was synthesized with 650 nm-excited 772 nm NIR PersL. The Y3+ doping in the Ca2+ lattice plays a key role in the PersL property. A charge compensation mechanism was proposed, in which Cr3+ in the Ti4+ lattice was stabilized by Y3+-doping while oxygen vacancies were generated to store the excitation energy at the same time. A thermal ionization mechanism might elucidate the red-light-excited NIR PersL of CTCY, which benefits from the perovskite structure of CaTiO3. CTCY has 120 times more intense red-light-excited PersL than Zn3Ga2Ge2O10:Cr. Its potential applications in luminescence anticounterfeiting and bioimaging were demonstrated using a visible/NIR dual-channel PersL flower painting and a CTCY-labeled bone screw for in situ reactivable PersL imaging using red light illumination instead of X-ray, respectively. This study not only provides a new NIR PersL material but also will add to our understanding in developing other potential red-light- or even NIR-activable PersL materials with perovskite-like structures.

Photoluminescence studies of Sr3P4O13: Eu3+ phosphor prepared by wet chemical method: Structural properties, charge compensation via alkali metal ions and Judd-Ofelt analysis

The Sr3P4O13:Eu3+ phosphors co-doped with alkali metal ions (A+ = Li+, Na+ and K+) were prepared by wet chemical method. The comparison with standard JCPDS data confirmed the formation of a triclinic crystalline phase with P-1(2) space group for the Eu3+ doped Sr3P4O13 phosphor and co-doped with alkali metal ions. The Li+ co-doped Sr3P4O13:Eu3+ phosphor has comparatively sharp and intense XRD patterns. The scanning electron microstructural analysis confirmed the formation of the particles size of 5 -50 μm. The comparative study of photoluminescence properties depicted that the peak positions were similar for all the prepared samples. The photoluminescence analysis of Sr3P4O13:Eu3+ phosphors show the emission in the red-orange region under the excitation of 394 nm (7F0→5L6) wavelength. Further, the charge compensation using alkali metal ions shows the larger photoluminescence intensity observed in the case of the Li+ co-doped Sr3P4O13:Eu3+ phosphors suggesting that the Li+ ion is better charge compensator among the studied alkali metal ions. Further, Judd-Ofelt (J-O) parameters were estimated for the Sr3P4O13:Eu3+ phosphors and co-doped with alkali metal ions in a series of samples. The comparison of Sr3P4O13:Eu3+ phosphors co-doped with alkali metal ions alongwith the J-O estimated parameters have been presented in the article.

Synergy of the heterojunction and defects engineering in Zr-doped TbFeO3@g-C3N4 photo-nanocatalyst towards enhanced visible-light-driven antibiotics degradation and H2 production

Environmental remediation and energy production are major concerns of the globe for sustainable development. Solar-driven photo nanocatalysts have shown great potential to be a suitable contender to solve these issues, however, their catalytic efficiency is the major concern which depends on the e−/h+ pair separation. The present study developed TbFe0.95Zr0.05O3/g-C3N4 heterostructure employing facile hydrothermal methods to promote e−/h+ pair separation. Though, TbFe0.95Zr0.05O3/g-C3N4 achieved the highest photo-degradation of 95.96 % for Norfloxacin (NOR) in 90 min, and 4864 μmol h−1g−1 of H2 evolution in 4 h under simulated visible-light, with 3.3, 2.8 and 2.1 times higher efficiency than pristine and doped catalysts (TbFeO3, g-C3N4 and TbFe0.95Zr0.05O3). The creation of oxygen vacancies (OVs) by Zr4+ doping at Fe3+ sites through charge compensation may increase catalytic efficiency, confirmed through X-ray photoelectron spectroscopy (XPS), and optical properties through Raman, and photoluminescence spectroscopy (PL). The catalyst works well throughout four cycles (85.19 % for NOR in the 4th cycle), demonstrating its chemical stability and cyclic potential. Thus, heterojunction and OVs synergistically enhance catalytic efficiency with higher activation in the visible solar spectrum and long e−/h+ charge separation lifetime.

Mn Doped MoO3 with Self-Assembled Nanoflowers Structure and Enhanced Gas Sensing Properties to Triethylamine

Increasing quality of life requires low power consumption and reliable gas sensing technology for real-time monitoring of the environment. Herein, based on the principle of ion compensation and charge compensation, Mn-doped MoO3 self-assembled nanoflowers were designed and prepared, and their gas-sensing performance were studied. Benefiting from abundant defective sites and surface chemical state changes, the sensor exhibits superior characteristics for triethylamine detection, including ultrahigh response (436.9), short response time (7 s), small detection limit (1 ppm), and remarkable selectivity. The gas-sensitive mechanism of M-MoO3 was explained from the points of view of charge compensation and ion compensation, and it was proved that the incorporation of Mn into MoO3 was an effective way to improve its gas sensitivity. This work provides a potential strategy for widespread triethylamine detection and provides new ideas for the design of high-performance sensors.

Study on the impact of cutoff voltage on structural and electrochemical stability of sodium-ion layered cathodes

NaNi1/3Fe1/3Mn1/3O2 is recognized for its relatively high theoretical specific capacity and operating voltage, rendering it a sodium-ion cathode material with significant commercial potential. A higher cutoff voltage typically enables more sodium ion deintercalation, thereby achieving higher capacity. However, this increased deintercalation can introduce challenges such as structural instability and side reactions with the electrolyte, leading to electrochemical performance degradation. This study focuses on the migration process of transition metal ions under conditions of high charging cutoff voltage and high sodium removal. At a voltage of 4.3 V, the migration of Ni ions facilitates more charge compensation but is accompanied by irreversible Ni migration, inducing an irreversible phase transition to the O’ phase. Conversely, at a cutoff voltage of 4.1 V, the P3 and O3 phases with high sodium removal demonstrate excellent cycling stability. The specific capacities before and after 150 cycles (at 0.5C) are 142.3 and 113.7 mAh/g, respectively, indicating a tolerable internal structural stress within these high sodium removal phases. This contrasts with the differentiated internal structural stresses generated by the P3, O3, and O’ phases during phase transitions at a cutoff voltage of 4.3 V. The research underscores the importance of regulating reversible crystal phases within the tolerance range of internal stress and avoiding irreversible crystal phases to enhance the cycling stability of cathode materials. These findings provide crucial insights for optimizing NNFMO cathode materials and hold significant implications for the design of high-performance, long-life sodium-ion batteries.

A three-in-one strategy of high-entropy, single-crystal, and biphasic approaches to design O3-type layered cathodes for sodium-ion batteries

O3-type layered oxides are promising cathodes for sodium-ion batteries (SIBs). However, severe volume changes, irreversible phase transitions, and sluggish Na+ ion transport kinetics lead to structural collapse and severe capacity loss. Herein, a three-in-one strategy “high entropy, single crystal, and biphase” is proposed to design O3-type layered cathodes for SIBs, which achieves enhanced structural stability and Na+ transport kinetics by the combination effect of multimetal high-entropy, the single crystal, and Li substitution. The as-prepared high-entropy oxide (HEO) cathode, Na(Fe1/6Co1/6Ni1/6Mn1/6Ti1/6)Li1/6O2, exhibits a high reversible capacity of 140.3 mAh g−1, robust cycling stability, exceptional rate capability (86 mAh g−1 at rates of 15C), excellent air-stability, and water-resistance ability. In situ X-ray diffraction reveals that the HEO cathode has highly reversible phase transitions and small volume change (ΔV=3.28 %). Ex situ X-ray absorption spectroscopy reveals that reversible Ni2+/Ni4+, Fe3+/Fe3.6+, and Co3+/Co3.6+ redox couples provide charge compensation for the high-entropy cathode at 2.0∼4.2 V. Notably, the full-cell battery based on the high-entropy cathode and hard carbon anode delivers a specific capacity of 134.3 mAh g−1 and an energy density of 390.8 Wh kg−1. This work provides valuable insights into the design of novel high-performance high-entropy cathodes for SIBs, highlighting a promising avenue for advancing rechargeable battery technology.

Effect of lithium concentration on the network connectivity of nuclear waste glasses

Structure of borosilicate glasses with varying Li2O contents were investigated using Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR), employing 6Li, 11B, 23Na, 27Al and 29Si nuclei. 11B MAS NMR revealed that increasing Li2O contents result in formation of [BO4]− sites at the expense of BO3. 11B{6Li} and 27Al{6Li} dipolar heteronuclear multiple quantum correlation (D-HMQC) NMR revealed Li as a charge compensator for anionic tetrahedral sites with increased Li. 11B{6Li} J-coupling mediated HMQC NMR suggested the possible association of Li with non-bridging oxygens on Q2 and Q3 sites, indicating its dual role in the glass network. 29Si and 23Na MAS NMR spectra showed depolymerisation of the silicate network and shortening of Na-O bond lengths with increased Li. NMR results are supported by Raman spectroscopy and thermal analysis that indicate depolymerisation of the silicate network and a reduction in glass transition temperature at higher Li content.

Leveraging photosensitive and thermally stable luminescent Ba2ZnWO6:Eu3+, M+ (M+= Na, K , and Li) nanophosphor for targeted non-invasive and stain-free visualization of cracked tooth syndrome

The cracked tooth syndrome poses a significant challenge in dentistry, thereafter untreated cases often lead to severe complications, such as pulpitis or complete tooth fracture, ultimately contributing to tooth loss. However, the conventional diagnostic methods to visualize microcracks in the tooth suffer from severe drawbacks, such as inaccurate cold stimulation, discomfort with probing, impractical staining techniques, and difficulty in distinguishing harmless craze lines from pathological cracks. To address this challenge, for the first time, we are proposing a novel approach by utilizing luminescent Ba2ZnWO6:Eu3+ (3 mol %), K+ (1 wt %) nanophosphor for improved imaging and diagnosis of cracked tooth syndrome. Herein, the double perovskite structured Ba2ZnWO6:Eu3+ (1–11 mol %), M+ (M+ = Na, K, and Li (1 wt %)) nanophosphors were synthesized via the sonochemical route. The photoluminescence emission spectra of the prepared Ba2ZnWO6:Eu3+ (1–11 mol %) nanophosphors displaying distinct peaks at 583, 595, 613, 662, and 720 nm, which ascribed to transitions from state 5D0 to 7FJ (J = 1–4) state of the Eu3+ ions, respectively. By adopting a strategic charge compensation mechanism, the enhancement in the luminescence emission intensity of about 1.5-fold was achieved after co-doping K+ (1 wt %) with Ba2ZnWO6:Eu3+ (3 mol %) nanophosphor. The photometric studies of the phosphors portray their orange-red emission with excellent quantum efficiency (82.52 %), and color purity (∼ 99 %). The emission intensity was sustained up to 73.71 % at 473 K, indicating excellent thermal stability of the phosphor. The in vitro cytotoxicity assessments of the optimized nanophosphor demonstrated its biocompatibility on normal non-malignant oral fibroblasts. The visualized microcracks in the tooth using optimized Ba2ZnWO6:Eu3+ (3 mol %), K+ (1 wt %) nanophosphor under UV excitation of UV 365 and 395 nm light revealed the orientation of microcracks, crack width, depth of the crack, and microcrack branching without any stain. The aforementioned results demonstrated that the proposed methodology paves the way for a new avenue in dental imaging technology with the potential to revolutionize and improve patient care outcomes.

LUMINESCENCE CHARACTERISTICS OF CASO4:TB,M (M=NA,K,RB) PHOSPHORS

In the present study, the investigation of complex luminescence terbium centres as well as the analysis of technological features of the synthesis of small-grained wide-gap CaSO :Tb3+ anhydrite phosphors containing 1% of Tb3+ and some amount of additional impurity ions (Na+, K+, Rb+) have been continued using the methods of optical and thermoactivation spectroscopy. Of particular interest was a contribution of calcium ions into formation of complex luminescence centres. Ca causes efficient dynamic hybridization of electronic states and influence on the formation of terbium and near-terbium electronic excitations. The excitation spectra of Tb3+-centre emission have been measured in the VUV spectral range at 77 or 300 K. The excitation band related to the lowest f–d transition of Tb3+ ions at ≈5.9 eV in CaSO4 undergoes broadening toward the long- wavelength side, when the radius of a charge compensator increases (K+→ Rb+). The band at 7.5–9 eV ascribed to the excitation of oxyanions has a different shape in CaSO4:Tb,K and CaSO4:Tb,Rb. Thermally stimulated luminescence (80–700 K) have been analyzed for a set of anhydrite phosphors previously irradiated by X-rays at 80 and 300 K. Keywords: CaSO , Tb3+, photoluminescence, thermoluminescence, vacuum ultraviolet spectroscopy.

Trace element analysis and luminescence behavior of quartz in pegmatites of the Tørdal Region, Norway

This publication presents a study on the mineral chemistry and luminescence properties of quartz samples from pegmatites of the Tørdal region in Norway. A total of 12 samples were analyzed using Secondary Ion Mass Spectrometry (SIMS), Electron Paramagnetic Resonance Spectroscopy (EPR), and Cathodoluminescence (CL) to gain insights into their trace element concentration and distribution as well as their luminescence behavior. The samples are characterized by different Cl emissions at 450 nm, 500 nm 650 nm and an additional shoulder at 390 nm, which is only partially visible due to the absorption of the glass optics. Of these luminescence bands, the 500 nm band is the most dominant in most samples and it is characterized by an initial blue-green luminescence, which is not stable under electron irradiation. Moreover, it is characterized by a heterogeneous distribution within the samples. This luminescence can be mostly assigned to [AlO4/M+]0 defects, with charge compensation mostly achieved by Li+. Analyses by EPR spectroscopy prove the dominance of structurally bound Al, Li, and Ti ions in the investigated samples. Further analyses using SIMS mapping demonstrate that Na and K are mainly bound to micro fractures or inclusions, suggesting a limited role in the compensation of the luminescence centers. Additionally, the SIMS mappings show that some samples contain Al-rich clusters of 10 to 20 μm in diameter, whereas other trace elements are characterized by a homogeneous distribution. These clusters correspond to bright luminescence areas in size and shape and could potentially indicate H+ compensated [AlO4/M+]0 defects.

Concurrent oxygen evolution reaction pathways revealed by high-speed compressive Raman imaging.

Transition metal oxides are state-of-the-art materials for catalysing the oxygen evolution reaction (OER), whose slow kinetics currently limit the efficiency of water electrolysis. However, microscale physicochemical heterogeneity between particles, dynamic reactions both in the bulk and at the surface, and an interplay between particle reactivity and electrolyte makes probing the OER challenging. Here, we overcome these limitations by applying state-of-the-art compressive Raman imaging to uncover concurrent bias-dependent pathways for the OER in a dense, crystalline electrocatalyst, α-Li2IrO3. By spatially and temporally tracking changes in stretching modes we follow catalytic activation and charge accumulation following ion exchange under various electrolytes and cycling conditions, comparing our observations with other crystalline catalysts (IrO2, LiCoO2). We demonstrate that at low overpotentials the reaction between water and the oxidized catalyst surface is compensated by bulk ion exchange, as usually only found for amorphous, electrolyte permeable, catalysts. At high overpotentials the charge is compensated by surface redox active sites, as in other crystalline catalysts such as IrO2. Hence, our work reveals charge compensation can extend beyond the surface in crystalline catalysts. More generally, the results highlight the power of compressive Raman imaging for chemically specific tracking of microscale reaction dynamics in catalysts, battery materials, or memristors.

Effects of ion mass transport on electrochemical reaction pathways in aluminum-anthraquinone batteries

Aluminum anodes and quinone-based organic cathodes couple as earth abundant, sustainable, and safe battery electrodes. However, different numbers of galvanostatic discharge plateaus have been observed in aluminum-quinone cells depending on the experimental conditions, a phenomenon that has not yet been explained and furthermore affects cell energy density. Here, in aluminum-anthraquinone batteries, we show that ion mass transport affects the electrochemical reaction pathway and controls the occurrence of either one or two reduction plateaus during galvanostatic discharge. The effects of electrode mass loading, porosity, rest periods, and cycling rates were analyzed on the reduction potential and relative specific capacity of the galvanostatic plateaus. When AlCl2+ cations charge compensate the electrochemically reduced carbonyl groups concurrently, a single reduction plateau is observed. When ion mass transport is limiting, sequential reduction and charge compensation of each carbonyl group results in two distinct reduction plateaus. The second plateau occurs at a potential approximately 0.3 V lower than the first, thus decreasing the cell energy density. The potential of the electrochemical oxidation reaction where AlCl2+ cations dissociate, however, is not affected. Ion mass transport is thus shown to be a critical variable that can control the electrochemical reaction pathway, redox potentials, and practical energy densities of aluminum-quinone batteries.

Dissolution of impurities in sodium gadolinium molybdate NaGd(MoO<sub>4</sub>)<sub>2</sub>

Impurity defects simulation in sodium-gadolinium molybdate NaGd(MoO4)2 was carried out using a method of interatomic potentials. The dissolution energies of tri-, di- and monovalent impurities were estimated. The dependences of the dissolution energy on the ionic radius of the impurity were plotted. For heterovalent substitutions, the most energetically favorable mechanism for charge compensation has been found, both due to intrinsic crystal defects and according to the conjugate isomorphism scheme. The positions of the most probable localization of defects are determined. The effect of disordering of sodium and gadolinium ions at equivalent positions on positional differences in the energy of defects is estimated. A comparison of the solubility of impurities in NaGd(MoO4)2 and its isostructural CaMoO4 indicates that, although isovalent substitutions are energetically more favorable than heterovalent ones, the mechanism of conjugate isomorphism, which ensures electrical neutrality, can equalize these processes.

Interlayer substitution enables air-stable and long-life O3-type cathode for sodium-ion batteries

The O3-type oxides (NaNi0.4Fe0.2Mn0.4O2 (NFM)) have been considered as the most commercially cathode material for high-energy-density sodium-ion batteries owing to their low price, good safety performance, and high energy density. However, their further development is seriously limited due to the complex phase transition, sluggish kinetics of Na+, and intrinsic air instability. Herein, an interlayer substituted NFM (IS-NFM) is constructed by a simple solid-state method with the introduction of alkaline-earth metal. The interlayer substitution will lead to the increase of oxygen content in the internal lattice, which will effectively suppress the irreversible phase transition during cycling and exposure to the air. In addition, the interlayer substitution effectively activated the charge compensation, leading to the mobilized cationic redox process and boosted de-/sodiated kinetic. Consequently, IS-NFM exhibits excellent capacity retention of 83.44 % at 1 C after 200 cycles and remarkable stability even at high voltage. After 15 days of exposure to the air, IS-NFM also delivers superior capacity retention (86.53 %, compared with 0.1 C) and cycling performance (82.70 % at 1 C after 200 cycles). Undoubtedly, the interlayer substitution strategy will expand a novel avenue for constructing air-stable and long-life O3-type oxides for commercial application.

Degree of Crystal Structure Distortion-Induced Tunable LiGaO2 Long Persistent Luminescence for Optical Information Encryption.

Tunable long persistent luminescence (LPL) phosphor materials have great potential for optoelectronic cryptographic applications. However, the mainstream techniques of modulating LPL generally have the characteristics of complex preparation processes, demanding crystal field environments, or expensive dopant ions, which restrict large-scale commercial application. Herein, we develop a simple, high-efficiency, and low-cost strategy to optimize the LPL of LiGaO2(LGO):Cu2+ by changing the sintering time to regulate the degree of crystal structure distortion. The Cu2+ as charge compensation will substantially enhance the emission intensity of LGO by a factor of 11.02 originating from the appropriate ionic size and coordination mode. Besides, the LPL time of LGO:Cu2+ can be extended effectively to 2 h by adjusting the sintering temperature and time (900 °C@24 h). The extension mechanism is that Li and Ga can be substituted for each other more easily and induce crystal structure distortion due to the special crystal structure of LGO, resulting in an optimal trap concentration in LGO:Cu2+. Thus, our findings provide a simple way to modulate long persistent luminescence and further consider their potential impact on optical information encryption.

The Utility of Adventitious Carbon for Charge Correction: A Perspective From a Second Multiuser Facility

ABSTRACTIn relation to debates in the recent literature on the utility and robustness of adventitious carbon for charge correction of X‐ray photoelectron spectra, the present work explores its application using 5 years' worth of data collected by the author. The data overwhelmingly show that regardless of spectrometer or charge compensation method, and but for a few exceptions where a secondary reference is preferrable, a C 1s value of 284.8 eV is suitable for electronically isolated samples.

H/D Isotope Effects in the Electrochemistry of Electrochromic Iron Hexacyanoruthenate

AbstractThe electrochemical deposition of iron hexacyanoruthenate (Fe−HCR) on gold electrodes was studied in electrolytes prepared with light and heavy water. Cyclic voltammetry of the material during preparation and after transfer to a precursor‐free solution exhibits two reductions peaks in H2O‐based electrolytes but only one reduction peak in D2O‐based electrolytes. The voltammetric behavior changes reversibly upon transfer of the material between D2O‐based and H2O‐based 1 mol L−1 KCl solutions. No clear structural differences between samples prepared in D2O and H2O were detected by means of X‐ray photoelectron spectroscopy (XPS) and polarization modulation infrared reflection absorption spectroscopy (PM IRRAS). We noted a relatively slow exchange of coordinated water and a fast exchange of zeolitic water. Using voltammetric experiments we could rule out simple effects of solution conductivity for K+, participation of H+/D+ in the charge compensation and surface effects on the observed dependence of the peak splitting on the isotopic composition of the solvent. The most likely reason for the observed behavior is the different structure of the H‐bonded water network of coordinated H2O and zeolitic H2O/D2O which is supported by the PM IRRAS data.

Strong Magnetic Exchange Interactions and Delocalized Mn-O States Enable High-Voltage Capacity in the Na-Ion Cathode P2-Na0.67[Mg0.28Mn0.72]O2.

The increased capacity offered by oxygen-redox active cathode materials for rechargeable lithium- and sodium-ion batteries (LIBs and NIBs, respectively) offers a pathway to the next generation of high-gravimetric-capacity cathodes for use in devices, transportation and on the grid. Many of these materials, however, are plagued with voltage fade, voltage hysteresis and O2 loss, the origins of which can be traced back to changes in their electronic and chemical structures on cycling. Developing a detailed understanding of these changes is critical to mitigating these cathodes' poor performance. In this work, we present an analysis of the redox mechanism of P2-Na0.67[Mg0.28Mn0.72]O2, a layered NIB cathode whose high capacity has previously been attributed to trapped O2 molecules. We examine a variety of charge compensation scenarios, calculate their corresponding densities of states and spectroscopic properties, and systematically compare the results to experimental data: 25Mg and 17O nuclear magnetic resonance (NMR) spectroscopy, operando X-band and ex situ high-frequency electron paramagnetic resonance (EPR), ex situ magnetometry, and O and Mn K-edge X-ray Absorption Spectroscopy (XAS) and X-ray Absorption Near Edge Spectroscopy (XANES). Via a process of elimination, we suggest that the mechanism for O redox in this material is dominated by a process that involves the formation of strongly antiferromagnetic, delocalized Mn-O states which form after Mg2+ migration at high voltages. Our results primarily rely on noninvasive techniques that are vital to understanding the electronic structure of metastable cycled cathode samples.

Progress in Sealed Lithium–Oxygen Batteries Based on the Oxygen Anion Charge Compensation Mechanism

Progress in Sealed Lithium–Oxygen Batteries Based on the Oxygen Anion Charge Compensation Mechanism

Perovskite Co-doping LaNiO3 quantum dots modified NiO/BaTiO3 transparent pn junction towards photovoltaic enhancement via bimetallic synergism

Transparent device in perovskite Co-LaNiO3 QDs modified NiO/BaTiO3 is prepared via an approach of sol-gel-annealing-chemical deposition method. The obtained NiO/Co-LaNiO3 QDs/BaTiO3 (NiO/BTO-LaCoNi-2) exhibits high transmittance of ∼80–85 %, obvious photovoltaic enhancement of ∼2.01 × 103-folds (PCE of ∼1.12 %) than NiO/BTO, stable output in ∼28000s. It can be mainly attributed to the perovskite Co-LaNiO3 QDs modification. Besides appropriate Fermi level and high quantum yield (DFT supporting), the Co-LaNiO3 QDs with extra carrier injecting/driving from synergism of charge compensation, bimetallic synergism and lattice distortion can improve the carrier kinetic equilibrium for PCE-transparency balance, meanwhile increasing the p-type conductivity via Cu vacancy/Ni vacancy/interstitial oxygen synergism. Moreover, the surface orderly nanosheets arrays can increase solar efficiency, while inorganic NiO, Co-LaNiO3 QDs, BaTiO3 and orderly interval with structural stability are beneficial for the actual applications.