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1.
Chem Sci ; 2024 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-39323528

RESUMO

The excellent photophysical and electrochemical properties of porphyrins have inspired widespread interest in the realm of electrochemiluminescence (ECL). The aggregation-caused deficiency of ECL emission in aqueous solution, however, still severely impedes further applications. Herein, a molecule with a donor-acceptor (D-A) configuration, ATPP-Cou, consisting of monoaminoporphyrin as an electron donor and coumarin as an electron acceptor, was designed as an ECL luminophore to address the susceptibility of the porphyrin to aggregation-caused quenching (ACQ) in aqueous solution. ATPP-Cou demonstrated a three-fold enhanced ECL signal compared to pristine ATPP. Despite the acknowledged significance of intramolecular charge transfer (ICT) in generating excited states in ECL, there is a lack of quantitative descriptions. Herein, intensity-modulated photocurrent spectroscopy (IMPS) and scanning photoelectrochemical microscopy (SPECM) were utilized to validate the influence of ICT on the enhancement performance of D-A type ECL molecules. Additionally, ATPP-Cou was also developed as a probe for the successful detection of Cu2+ in aqueous solution. The present study not only enriches the repertoire of efficient porphyrin-based ECL luminophores applicable in aqueous environments but also exemplifies the successful integration of novel measurement techniques to provide more comprehensive insights into the underlying mechanisms responsible for improved ECL performance.

2.
Artigo em Inglês | MEDLINE | ID: mdl-39276846

RESUMO

BACKGROUND: Primary glenohumeral osteoarthritis in young patients poses challenging treatment decisions. Arthroplasty options have different failure profiles and implant survivorship patterns. This registry study aims to analyze the cumulative per cent revision rate (CPR) of different types of arthroplasties conducted for primary osteoarthritis in patients under 55 years of age. METHODS: This comparative observational national registry study included all shoulder arthroplasty for osteoarthritis in patients under 55 years of age undertaken between January 1st, 2005, and December 31st, 2022. Partial hemi resurfacing and hemi stemless procedures were excluded. The cumulative percentage of revision (CPR) was determined using Kaplan-Meier estimates of survivorship and hazard ratios (HR) from Cox proportional hazard models adjusted for gender. Reasons for revision of each type of arthroplasty and cumulative incidence of revision diagnoses were analyzed. RESULTS: 2111 primary shoulder arthroplasties were compared. Glenoid erosion is the predominant cause of revision for humeral resurfacing (29.8%) and hemiarthroplasty (35.5%). Instability is the predominant cause of revision for stemmed anatomic total shoulder arthroplasty (ATSA) and reverse total shoulder arthroplasty (RTSA), while loosening is the predominant cause of revision for stemless ATSA. The 6-year CPR is 12.8% for humeral resurfacing (HRA), 14.1% for hemiarthroplasty (HA), 12.4% for stemmed (ATSA), 7.0% for stemless ATSA, and 6.5% for (RTSA). Stemmed ATSA had a higher revision rate than RTSA (entire period HR=2.04 (95% confidence interval (CI) 1.16, 3.57), p=0.012). In contrast, the revision rate of stemless ATSA was not different from RTSA (HR =1.05 (95% CI 0.51, 2.19), p=0.889). Males outnumber females for all shoulder arthroplasty categories. DISCUSSION: RTSA and stemless ATSA are viable options in young patients with primary osteoarthritis. Their short-to medium-term revision rates are comparable to those of older patients and lower than those associated with HRA, HA, and stemmed ATSA. CONCLUSION: In the predominantly male patient population under the age of 55, reverse shoulder arthroplasty and stemless ATSA have a lower short-term revision risk than stemmed ATSA.

3.
PLoS One ; 19(5): e0304446, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38814927

RESUMO

In privacy protection methods based on location services, constructing anonymous areas using location information shared by collaborative users is the main method. However, this collaborative process not only increases the risk of mobile users' location privacy being leaked, but also reduces positioning accuracy. In response to this problem, we propose a balancing strategy, which transforms the problem of protecting mobile users' location privacy and improving positioning accuracy into a balance issue between location privacy and positioning accuracy. The cooperation of mobile users with different collaborating users is then modeled as an objective optimization problem, and location privacy and positioning accuracy are evaluated separately to make different selection strategies. Finally, an optimization function is constructed to select the optimal selection strategies. Experimental results show that our proposed strategy can effectively achieve the balance between location privacy and positioning accuracy.


Assuntos
Privacidade , Humanos , Algoritmos , Modelos Teóricos , Sistemas de Informação Geográfica
4.
Angew Chem Int Ed Engl ; 63(3): e202315763, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-38029382

RESUMO

Limited charge separation/transport efficiency remains the primary obstacle of achieving satisfying photoelectrochemical (PEC) water splitting performance. Therefore, it is essential to develop diverse interfacial engineering strategies to mitigate charge recombination. Despite obvious progress having been made, most works only considered a single-side modulation in either the electrons of conduction band or the holes of valence band in a semiconductor photoanode, leading to a limited PEC performance enhancement. Beyond this conventional thinking, we developed a novel coupling modification strategy to achieve a composite electrode with bidirectional carrier transport for a better charge separation, in which Ti2 C3 Tx MXene quantum dots (MQDs) and α-Fe2 O3 nanodots (FO) are anchored on the surface of ZnIn2 S4 (ZIS) nanoplates, resulting in markedly improved PEC water splitting of pure ZIS photoanode. Systematic studies indicated that the bidirectional charge transfer pathways were stimulated due to MQDs as "electron extractor" and S-O bonds as carriers transport channels, which synergistically favors significantly enhanced charge separation. The enhanced kinetic behavior at the FO/MQDs/ZIS interfaces was systematically and quantitatively evaluated by a series of methods, especially scanning photoelectrochemical microscopy. This work may deepen our understanding of interfacial charge separation, and provide valuable guidance for the rational design and fabrication of high-performance composite electrodes.

5.
Anal Chem ; 96(1): 110-116, 2024 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-38150391

RESUMO

BiVO4 is a promising photoanode for photoelectrochemical (PEC) water splitting but suffers from high charge carrier recombination and sluggish surface water oxidation kinetics that limit its efficiency. In this work, a model of sulfur-incorporated FeOOH cocatalyst-loaded BiVO4 was constructed. The composite photoanode (BiVO4/S-FeOOH) demonstrates an enhanced photocurrent density of 3.58 mA cm-2, which is 3.7 times higher than that of the pristine BiVO4 photoanode. However, the current explanations for the generation of enhanced photocurrent signals through the incorporation of elements and cocatalyst loading remain unclear and require further in-depth research. In this work, the hole transfer kinetics were investigated by using a scanning photoelectrochemical microscope (SPECM). The results suggest that the incorporation of sulfur can effectively improve the charge transfer capacity of FeOOH. Moreover, the oxygen evolution reaction model provides evidence that S-doping can induce a "fast" surface catalytic reaction at the cocatalyst/solution interface. The work not only presents a promising approach for designing a highly efficient photoanode but also offers valuable insights into the role of element doping in the PEC water-splitting system.

6.
Mater Horiz ; 10(12): 5656-5665, 2023 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-37766462

RESUMO

Thermally conductive materials (TCMs) are highly desirable for thermal management applications to tackle the "overheating" concerns in the electronics industry. Despite recent progress, the development of high performance TCMs integrated with an in-plane thermal conductivity (TC) higher than 50.0 W (m K)-1 and a through-plane TC greater than 10.0 W (m K)-1 is still challenging. Herein, self-standing liquid metal@boron nitride (LM@BN) bulks with ultrahigh in-plane TC and through-plane TC were reported for the first time. In the LM@BN bulks, LM could serve as a bonding and thermal linker among the oriented BN platelets, thus remarkably accelerating heat transfer across the whole system. Benefiting from the formation of a unique structure, the LM@BN bulk achieved an ultrahigh in-plane TC of 82.2 W (m K)-1 and a through-plane TC of 20.6 W (m K)-1, which were among the highest values ever reported for TCMs. Furthermore, the LM@BN bulks exhibited superior compressive and leakage-free performances, with a high compressive strength (5.2 MPa) and without any LM leakage even after being crushed. It was also demonstrated that the excellent TCs of the LM@BN bulks made them effectively cool high-power light emitting diode modules. This work opens up one promising pathway for the development of high-performance TCMs for thermal management in the electronics industry.

7.
J Colloid Interface Sci ; 646: 238-244, 2023 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-37196497

RESUMO

Bismuth vanadate (BiVO4) is a promising nanomaterial for photoelectrochemical (PEC) water oxidation. However, the serious charge recombination and sluggish water oxidation kinetics limit its performance. Herein, an integrated photoanode was successfully constructed by modifying BiVO4 (BV) with In2O3 (In) layer and further decorating amorphous FeNi hydroxides (FeNi). The BV/In/FeNi photoanode exhibited a remarkable photocurrent density of 4.0 mA cm-2 at 1.23 VRHE, which is approximately 3.6 times larger than that of pure BV. And the water oxidation reaction kinetics has an over 200% increased. This improvement was mainly because the formation of BV/In heterojunction inhibited charge recombination, and the decoration of cocatalyst FeNi facilitated the water oxidation reaction kinetics and accelerated hole transfer to electrolyte. Our work provides another possible route to develop high-efficiency photoanodes for practical applications in solar conversion.

8.
BMC Pregnancy Childbirth ; 23(1): 190, 2023 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-36934251

RESUMO

BACKGROUND: Bacterial contamination may cause loss of or damage to cultured oocytes or embryos, resulting in the lack of transplantable embryos during IVF embryo culture. However, there are few reports about IVF embryo contamination caused by embryology laboratories. In this work, we evaluated clinical pregnancy outcomes and the risk of maternal and infant complications after embryo contamination caused by environmental pollution during IVF. METHODS: The authors retrospectively analyzed 2490 IVF-ET ovulation induction therapy cycles in the Reproductive Center of Yichang Central People's Hospital from January 2015 to May 2022. According to the presence or absence of embryo culture medium contamination, the two groups were divided into an embryo contamination cycle and a nonembryo contamination cycle. The primary outcome parameters were the characteristics and progress of embryo culture medium contamination. Embryo laboratory outcomes, pregnancy outcomes, and maternal and infant complications were secondary outcome parameters. RESULTS: One case of embryo contamination originated from semen contamination. The remaining 15 cases involved environmental contamination outbreaks in embryo culture chambers, caused by Staphylococcus pasteuri. Compared with conventional uncontaminated IVF cycles, the 15 cases of contaminated embryo cycles showed no significant difference in embryo laboratory outcomes, pregnancy outcomes, or maternal and infant complications except for a slightly higher rate of fetal growth retardation. Ultimately, 11 live-born infants were successfully delivered, of which 2 were premature. The remaining 4 patients did not become pregnant after 1-2 transfers due to a lack of transferable embryos. CONCLUSION: When the embryo culture medium is contaminated due to the environmental contamination of the IVF culture room, it is feasible to perform daily rapid rinsing of the culture medium and avoid blastocyst culture as remedial treatment. However, the long-term impact on offspring needs further prospective research.


Assuntos
Fertilização in vitro , Laboratórios , Gravidez , Feminino , Humanos , Fertilização in vitro/métodos , Estudos Retrospectivos , Resultado da Gravidez/epidemiologia , Poluição Ambiental , Taxa de Gravidez
9.
Anal Chem ; 94(23): 8426-8432, 2022 06 14.
Artigo em Inglês | MEDLINE | ID: mdl-35657752

RESUMO

Owing to their almost similarities in size, shape, and chemical reactivity, effectively distinguishing deuteroxide (D2O) in water (H2O) remains an ongoing challenge, and the examples of a D2O probe are still quite scarce. Herein, since H2O can decrease the lifetime of a singlet oxygen as a vital intermediate and an H/D exchange in the luminescence process of porphyrins, we systematically investigated the enhanced ultraviolet-visible (UV-vis), photoluminescence (PL), and electrochemiluminescence (ECL) of water-soluble tetrakis(carboxphenyl)porphyrin (TCPP) in D2O. The findings showed that these luminescent properties had been greatly enhanced with the increase of the D2O fraction in water. Consequently, we first developed the highly facile methods of detecting D2O in H2O by the UV-vis, PL, and ECL of TCPP, respectively. Impressively, the ECL analysis exhibited a great superiority with a lower detection limit of 0.29 nM. The work not only achieves the challenging task of distinguishing between H2O and D2O but also provides a unique strategy to enhance the luminescent performance of porphyrin.


Assuntos
Porfirinas , Luminescência , Medições Luminescentes/métodos , Porfirinas/química , Oxigênio Singlete , Água/química
10.
Anal Chem ; 94(23): 8539-8546, 2022 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-35658420

RESUMO

Photoelectrochemical (PEC) water splitting technology is a promising strategy toward producing sustainable hydrogen fuel. However, it is an essential bottleneck to reduce severe charge recombination for the improvement of PEC performance. Construction of heterojunction systems, such as Z-scheme and type II heterojunctions, could efficiently boost charge separation, whereas the mechanism of charge separation is still ambiguous. We describe herein a charge transfer system designed with Bi2WO6/Bi2S3 (BWO/BS) as a prototype. In this system, Au nanoparticles act as charge relays to engineer a charge transfer pathway, and the obtained BWO/Au/BS photoanode achieves a remarkable photocurrent density of 0.094 mA cm-2 at 1.23 V versus reversible hydrogen electrode (vs RHE), over approximately 1.2 and 2.3 times larger than those of BWO/BS/Au and BWO, exhibiting long-term photostability. More importantly, scanning photoelectrochemical microscopy (SPECM) and intensity-modulated photocurrent spectroscopy (IMPS) studies are performed to in situ-capture the photogenerated hole during the PEC process. Operando analysis reveals that the Z-scheme BWO/Au/BS system (1.33 × 10-2 cm s-1) exhibits higher charge transfer kinetics compared to the type II BWO/BS/Au heterostructure (0.85 × 10-2 cm s-1) while efficiently suppressing charge recombination for optimized PEC activity. Note that this smart strategy can also be extended to other semiconductor-based photoanodes such as BiVO4. Our study offers an effective pathway for the rational design of highly efficient charge separation for solar conversion based on water splitting.

11.
Small ; 18(20): e2107938, 2022 05.
Artigo em Inglês | MEDLINE | ID: mdl-35434918

RESUMO

Semiconductor/co-catalyst coupling is considered as a promising strategy to enhance the photoelectrochemical (PEC) conversion efficiency. Unfortunately, this model system is faced with a serious interface recombination problem, which limits the further improvement of PEC performances. Here, a FeNiOOH co-catalyst with abundant oxygen vacancies on BiVO4 is fabricated through simple and economical NaBH4 reduction to accelerate hole transfer and achieve efficient electron-hole pair separation. The photocurrent of the BV (BiVO4 )/Vo-FeNiOOH system is more than four times that of pure BV. Importantly, the charge transfer kinetics and charge carrier recombination process are studied by scanning photoelectrochemical microscopy and intensity modulated photocurrent spectroscopy in detail. In addition, the oxygen vacancy regulation proposed is also applied successfully to other semiconductors (Fe2 O3 ), demonstrating the applicability of this strategy.


Assuntos
Oxigênio , Semicondutores , Catálise , Oxigênio/química
12.
J Colloid Interface Sci ; 615: 318-326, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35144232

RESUMO

Photoelectrochemical (PEC) water splitting is an attractive strategy to convert and store of intermittent solar power into fuel energy. However, the detrimental charge recombination of photogenerated electrons and holes severely limits its efficiency. Despite electrocatalyst loading can obviously improve the PEC conversion efficiency, current systems still suffer from high recombination owing to the surface states. Herein, an interface "repairing" strategy is proposed to suppress the recombination at the semiconductor/electrocatalyst interface. NiOx layer acts as an interfacial repairing layer to efficiently extract photogenerated charge carriers and eliminate the surface states via high hole-transfer kinetics rather than as a traditional electrocatalyst. As expected, the resulting repaired system yields an impressive photocurrent density of 4.58 mA cm-2 at 1.23 V (vs. RHE), corresponding to a more than three-fold increase compared to BiVO4 (1.40 mA cm-2). Our work offers an appealing maneuver to improve the water oxidation performance for the semiconductor/electrocatalyst coupling system.

13.
Anal Chem ; 93(27): 9621-9627, 2021 07 13.
Artigo em Inglês | MEDLINE | ID: mdl-34197082

RESUMO

Manganese dioxide nanosheets combined with cysteine-assisted emitting manganese dioxide nanospheres (Cys-MnO2 nanospheres) is fabricated for the first time as an "off-on" fluorescence detection platform for glutathione (GSH). In this sensing system, Cys-MnO2 nanospheres served as energy donors, while MnO2 nanosheets were used as both energy acceptors and recognition units. MnO2 nanosheets can effectively quench the fluorescence of Cys-MnO2 nanospheres through the fluorescence resonance energy transfer (FRET). The addition of GSH could reduce MnO2 nanosheets into Mn2+, disrupting the FRET process and restoring the fluorescence of Cys-MnO2 nanospheres. Under the optimum conditions, the "switch-on" platform we established has a wide response to GSH with a range of 5-50 µM and 150-800 µM, as well as a superior specificity. Importantly, all components of the sensor are nontoxic, biocompatible, easily prepared, and have a high utilization of raw materials. Moreover, the sensing system achieved satisfactory results in human serum, showing a tremendous potential in the field of biomedicine.


Assuntos
Glutationa/análise , Compostos de Manganês , Nanosferas , Cisteína , Transferência Ressonante de Energia de Fluorescência , Humanos , Limite de Detecção , Óxidos
14.
Anal Chem ; 93(30): 10619-10626, 2021 08 03.
Artigo em Inglês | MEDLINE | ID: mdl-34283563

RESUMO

Luminol, as a classical luminophore, plays a crucial role in electrochemiluminescence (ECL). However, the traditional luminol-H2O2 ECL system suffers from the self-decomposition of H2O2 at ambient temperature, which hinders its further application in quantitative analysis. In this work, for the first time, we developed atomically gold-supported two-dimensional VO2 nanobelts (Au/VO2) as an advanced co-reaction promoter to speed up the reduction of dissolved oxygen to superoxide radicals (O2•-), which react with the luminol anion radical and greatly promote the ECL emission. The ECL resonance energy transfer (ECL-RET) between the hollow manganese dioxide nanospheres and luminol results in a conspicuously decreased ECL signal response, and in the presence of glutathione (GSH), effective redox reaction between manganese dioxide and GSH restores the ECL signal. As a consequence, the designed sensor based on ECL-RET-assisted Au/VO2 signal amplification showed outstanding performance for "signal-on" detection of GSH in the concentration range of 10-3 to 10-10 M, and the detection limit was as low as 0.03 nM. The ECL sensor displayed excellent specificity and was successfully utilized to target GSH in real human serum samples. Importantly, this work not only highlights a powerful avenue for constructing an ultrasensitive ECL sensor for GSH but also provides some inspiration for the further design of high-performance co-reaction accelerators using the ECL technique.


Assuntos
Técnicas Biossensoriais , Nanopartículas Metálicas , Técnicas Eletroquímicas , Transferência de Energia , Ouro , Humanos , Peróxido de Hidrogênio , Limite de Detecção , Medições Luminescentes , Luminol
15.
ACS Appl Mater Interfaces ; 13(28): 32743-32752, 2021 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-34228441

RESUMO

In the past 10 years, many fluorescent probes have been developed to recognize G-quadruplexes (G4s) since G4s play an important role in biological systems. However, the selectivity and sensitivity of existing probes for G4s limit their further applications. Herein, we design and synthesize a new probe (TOVJ) by introducing 9-vinyljulolidine into TO. The new probe exhibits almost no fluorescence in an aqueous solution. Upon interacting with G4s, especially the antiparallel G4s, the fluorescence intensity was greatly enhanced (maximum 2742-fold) with a large Stokes shift of 198 nm and the maximum emission peak at 694 nm (near-infrared region). TOVJ showed high sensitivity and selectivity to G4s over other DNA topologies (ssDNA/dsDNA), especially to antiparallel G4s. For antiparallel human telomere G4 detection, the limits of detection of Hum24 and 22AG Na+ were as low as 164 and 231 pM, respectively. This indicates that TOVJ is a highly sensitive fluorescence sensor that can be effectively used for antiparallel human telomere G4 detection. The result of live-cell imaging showed that TOVJ could enter live cells and locate in the mitochondria.


Assuntos
DNA/análise , Corantes Fluorescentes/química , Quadruplex G , Quinolinas/química , Quinolizinas/química , Telômero/química , DNA/genética , Corantes Fluorescentes/síntese química , Células HeLa , Humanos , Limite de Detecção , Microscopia de Fluorescência , Quinolinas/síntese química , Quinolizinas/síntese química , RNA/análise , RNA/genética
16.
Eur J Pharmacol ; 905: 174187, 2021 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-34048738

RESUMO

To keep fast proliferation, tumor cells are exposed to higher oxidative stress than normal cells and they upregulate the amount of some antioxidants such as glutathione (GSH) against reactive oxygen species to maintain the balance. This phenomenon is severe in hypoxic tumor cells. Although researchers have proposed a series of treatment strategies based on regulating the intracellular reactive oxygen species level, few of them are related to the hypoxic tumor. Herein, a novel organic compound (PLC) was designed by using lysine as a bridge to connect two functional small molecules, a hypoxia-responsive nitroimidazole derivative (pimonidazole) and a pH-responsive cinnamaldehyde (CA) derivative. Then, the oxidative stress amplifying ability of PLC in hypoxic tumor cells was evaluated. The acidic microenvironment of tumor can trigger the release of CA to produce reactive oxygen species. Meanwhile, large amount of nicotinamide adenine dinucleotide phosphate (NADPH) can be consumed to decrease the synthesis of GSH during the bio-reduction process of the nitro group in PLC under hypoxic conditions. Therefore, the lethal effect of CA can be amplified for the decrease of GSH. Our results prove that this strategy can significantly enhance the therapeutic effect of CA in the hypoxic tumor cells.


Assuntos
Acroleína/análogos & derivados , Antineoplásicos Fitogênicos/farmacologia , Neoplasias/tratamento farmacológico , Nitroimidazóis/farmacologia , Estresse Oxidativo/efeitos dos fármacos , Hipóxia Tumoral , Acroleína/síntese química , Acroleína/química , Acroleína/farmacologia , Animais , Antineoplásicos Fitogênicos/síntese química , Antineoplásicos Fitogênicos/química , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Glutationa/metabolismo , Humanos , Concentração de Íons de Hidrogênio , Camundongos , NADP/metabolismo , Neoplasias/metabolismo , Nitroimidazóis/síntese química , Nitroimidazóis/química , Espécies Reativas de Oxigênio/metabolismo , Microambiente Tumoral
17.
J Colloid Interface Sci ; 597: 206-214, 2021 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-33872877

RESUMO

Photocatalysis utilizing solar energy is a promising strategy for mitigating energy crisis and environmental pollution. Exploring a cost-effective, stable, eco-friendly, and efficient photocatalytic system is extremely urgent. Herein, copper encapsulated within nitrogen-doped carbon nanosphere (Cu@NC) possessing a unique core-shell structure with high catalytic activity was prepared by ion-exchange and pyrolysis using resin as support. The protective carbon shell can prevent the leaching of metal ions and deactivation of the catalyst. Benefiting from the special structure, Cu@NC exhibited excellent activity and durability toward the degradation of tetracycline by the activation of peroxymonosulfate (PMS). The radical trapping experiments and electron spin resonance analyses were applied to elucidate the main reactive species. This work highlights the great potential of Cu@NC core-shell nanosphere as photocatalyst, which provides a new opportunity for the remediation of environmental pollution.

18.
ChemSusChem ; 14(5): 1414-1422, 2021 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-33452868

RESUMO

Detrimental charge recombination at photoanode/electrolyte junctions severely impedes photoelectrochemical (PEC) performance. The deposition of cobalt phosphate (CoPi) onto photoanodes is an efficient approach to achieve high PEC efficiency. However, achieving performances at the required remains a huge challenge, owing to the passivation effect of CoPi. In this study, function-tunable strategy, whereby the passivation role is switched with the activation role, is exploited to modulate PEC performance through simultaneous activation of interface charge transfer and surface catalysis. By depositing nickel-doped CoPi onto a BiVO4 (BV) substrate, the integrated system (BV/Ni1 Co7 Pi) exhibits a remarkable photocurrent density (4.15 mA cm-2 ), which is a 4.6-fold increase relative to BV (0.90 mA cm-2 ). Moreover, the satisfactory performance can be also achieved on α-Fe2 O3 photoanode. These findings provide guidance for improving the efficiency of CoPi on photoanodes for PEC water oxidation.

19.
J Colloid Interface Sci ; 588: 31-39, 2021 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-33387823

RESUMO

The desired photoelectrochemical performance can be achieved by temperature regulation, but the nature for this improvement remains a controversial topic. Herein, we employed BiVO4/CoOx as a typical model system, and explored the fate of photogenerated holes at the different interfaces among BiVO4/CoOx/electrolyte by means of intensity modulated photocurrent spectroscopy (IMPS), scanning photoelectrochemical microscopy (SPECM) and traditional electrocatalysis characterization methods. Systematic quantitative analysis of the kinetics of photogenerated holes transfer at the BiVO4/CoOx interface under illumination and surface water oxidation at the CoOx/electrolyte interface in the dark indicates that increasing temperature could not only enhance the surface catalytic reaction kinetics but also facilitate the interfacial charge transfer. As expected, the integrated system exhibited a remarkable photocurrent density of 3.6 mA cm-2 (1.23 VRHE, AM 1.5G, 45 °C), which is approximately 2.1 times higher than that of BiVO4/CoOx (15 °C). This work provides a promising strategy for achieving efficient photoelectrochemical water splitting.

20.
Angew Chem Int Ed Engl ; 60(7): 3504-3509, 2021 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-33105064

RESUMO

Depositing a transition-metal hydroxide (TMH) layer on a photoanode has been demonstrated to enhance photoelectrochemical (PEC) water oxidation. However, the controversial understanding for the improvement origin remains a key challenge to unlock the PEC performance. Herein, by taking BiVO4 /iron-nickel hydroxide (BVO/Fx N4-x -H) as a prototype, we decoupled the PEC process into two processes including charge transfer and surface catalytic reaction. The kinetic information at the BVO/Fx N4-x -H and Fx N4-x -H/electrolyte interfaces was systematically evaluated by employing scanning photoelectrochemical microscopy (SPECM), intensity modulated photocurrent spectroscopy (IMPS) and oxygen evolution reaction (OER) model. It was found that Fx N4-x -H acts as a charge transporter rather than a sole electrocatalyst. PEC performance improvement is mainly ascribed to the efficient suppression of charge recombination by fast hole transfer kinetics at BVO/Fx N4-x -H interface.

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