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Heavy-duty diesel vehicles (HDDVs) significantly contribute to atmospheric nitrogen oxides (NOX) and black carbon (BC), with high emitters within the HDDV fleet impacting the total emissions. However, emission patterns and contributions of high emitters are rarely explored from a fleet-perspective. We investigated NOX and BC emission factors (EFs) from 1925 HDDVs in Shenzhen by the plume-chasing method, and found that the fleet-average EFs decreased with stricter emission standards. Unexpectedly, the average NOX EF for the China IV fleet was comparable with that for the China III fleet due to possible ineffective aftertreatment in high-emitter sectors of China IV HDDVs. Decreasing trend in average NOX EF since 2017 reflected the effective emission controls by the implementation of China V standard. Besides, semi-trailer tractors exhibited a higher incidence of NOX over-emissions, whereas BC high emitters were more pronounced in box trucks. Total NOX and BC emissions from HDDVs in Shenzhen were revisited, reaching 54.0 and 1.1 Gg·yr-1, with updated NOX EF correcting a 26.2 % underestimation in national guidelines. Notably, eliminating high emitters yields greater emission reduction benefits than merely retiring old HDDVs, with BC reduction outpacing NOX. This study provides new insights into the implementation of targeted emission reduction measures for HDDVs.
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Inverted (pin) perovskite solar cells (PSCs) afford improved operating stability in comparison to their nip counterparts but have lagged in power conversion efficiency (PCE). The energetic losses responsible for this PCE deficit in pin PSCs occur primarily at the interfaces between the perovskite and the charge-transport layers. Additive and surface treatments that use passivating ligands usually bind to a single active binding site: This dense packing of electrically resistive passivants perpendicular to the surface may limit the fill factor in pin PSCs. We identified ligands that bind two neighboring lead(II) ion (Pb2+) defect sites in a planar ligand orientation on the perovskite. We fabricated pin PSCs and report a certified quasi-steady state PCE of 26.15 and 24.74% for 0.05- and 1.04-square centimeter illuminated areas, respectively. The devices retain 95% of their initial PCE after 1200 hours of continuous 1 sun maximum power point operation at 65°C.
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Perovskite solar cells (PSCs) consisting of interfacial two- and three-dimensional heterostructures that incorporate ammonium ligand intercalation have enabled rapid progress toward the goal of uniting performance with stability. However, as the field continues to seek ever-higher durability, additional tools that avoid progressive ligand intercalation are needed to minimize degradation at high temperatures. We used ammonium ligands that are nonreactive with the bulk of perovskites and investigated a library that varies ligand molecular structure systematically. We found that fluorinated aniliniums offer interfacial passivation and simultaneously minimize reactivity with perovskites. Using this approach, we report a certified quasi-steady-state power-conversion efficiency of 24.09% for inverted-structure PSCs. In an encapsulated device operating at 85°C and 50% relative humidity, we document a 1560-hour T85 at maximum power point under 1-sun illumination.
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The exploration of thermoelectric materials is challenging considering the large materials space, combined with added exponential degrees of freedom coming from doping and the diversity of synthetic pathways. Here, historical data is incorporated, and is updated using experimental feedback by employing error-correction learning (ECL). This is achieved by learning from prior datasets and then adapting the model to differences in synthesis and characterization that are otherwise difficult to parameterize. This strategy is thus applied to discovering thermoelectric materials, where synthesis is prioritized at temperatures <300 °C. A previously unexplored chemical family of thermoelectric materials, PbSe:SnSb, is documented, finding that the best candidate in this chemical family, 2 wt% SnSb doped PbSe, exhibits a power factor more than 2× that of PbSe. The investigations herein reveal that a closed-loop experimentation strategy reduces the required number of experiments to find an optimized material by a factor as high as 3× compared to high-throughput searches powered by state-of-the-art machine-learning (ML) models. It is also observed that this improvement is dependent on the accuracy of the ML model in a manner that exhibits diminishing returns: once a certain accuracy is reached, factors that are instead associated with experimental pathways begin to dominate trends.
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Owing to its biotoxicity and inductive effect on photochemical pollution, atmospheric peroxyacetyl nitrate (PAN), which is a typical product of atmospheric photochemical reactions, has attracted much research attention. However, to the best of our knowledge, few comprehensive studies have been conducted on the seasonal variation and key influencing factors of PAN concentrations in southern China. In this study, PAN, ozone (O3), precursor volatile organic compound (VOC), and other pollutant concentrations were measured online for 1 year (from October 2021 to September 2022) in Shenzhen, a megacity in the Greater Bay Area of China. The average concentrations of PAN and peroxypropionyl nitrate (PPN) were 0.54 and 0.08 parts per billion (ppb), and the maximum hourly concentrations reached 10.32 and 1.01 ppb, respectively. The results of the generalized additive model (GAM) showed that the atmospheric oxidation capacity and precursor concentration were the most important factors affecting the PAN concentration. According to the steady-state model, the average cumulative contribution to the peroxyacetyl (PA) radical formation rate by six major carbonyl compounds was calculated at 4.2 × 106 molecules cm-3 s-1, and acetaldehyde (63.0 %) and acetone (13.9 %) contributed the most. Furthermore, the photochemical-age-based parameterization method was used to analyze the source contributions of carbonyl compounds and PA radicals. The results showed that although the primary anthropogenic (40.2 %), biogenic (27.8 %), and secondary anthropogenic (16.4 %) sources were the most important contributors of PA radicals, the biogenic and secondary anthropogenic source contributions both increased considerably in summer, and the cumulative proportion of both sources reached ~70 % in July. In addition, a comparison of PAN pollution processes in different seasons revealed that in summer and winter, the PAN concentration was predominantly limited by precursors and meteorological parameters, such as light intensity, respectively.
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Contaminantes Atmosféricos , Ozono , Compuestos Orgánicos Volátiles , Estaciones del Año , Contaminantes Atmosféricos/análisis , China , Ozono/análisis , Compuestos Orgánicos Volátiles/análisis , Monitoreo del AmbienteRESUMEN
The tunable bandgaps and facile fabrication of perovskites make them attractive for multi-junction photovoltaics1,2. However, light-induced phase segregation limits their efficiency and stability3-5: this occurs in wide-bandgap (>1.65 electron volts) iodide/bromide mixed perovskite absorbers, and becomes even more acute in the top cells of triple-junction solar photovoltaics that require a fully 2.0-electron-volt bandgap absorber2,6. Here we report that lattice distortion in iodide/bromide mixed perovskites is correlated with the suppression of phase segregation, generating an increased ion-migration energy barrier arising from the decreased average interatomic distance between the A-site cation and iodide. Using an approximately 2.0-electron-volt rubidium/caesium mixed-cation inorganic perovskite with large lattice distortion in the top subcell, we fabricated all-perovskite triple-junction solar cells and achieved an efficiency of 24.3 per cent (23.3 per cent certified quasi-steady-state efficiency) with an open-circuit voltage of 3.21 volts. This is, to our knowledge, the first reported certified efficiency for perovskite-based triple-junction solar cells. The triple-junction devices retain 80 per cent of their initial efficiency following 420 hours of operation at the maximum power point.
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Lewis base molecules that bind undercoordinated lead atoms at interfaces and grain boundaries (GBs) are known to enhance the durability of metal halide perovskite solar cells (PSCs). Using density functional theory calculations, we found that phosphine-containing molecules have the strongest binding energy among members of a library of Lewis base molecules studied herein. Experimentally, we found that the best inverted PSC treated with 1,3-bis(diphenylphosphino)propane (DPPP), a diphosphine Lewis base that passivates, binds, and bridges interfaces and GBs, retained a power conversion efficiency (PCE) slightly higher than its initial PCE of ~23% after continuous operation under simulated AM1.5 illumination at the maximum power point and at ~40°C for >3500 hours. DPPP-treated devices showed a similar increase in PCE after being kept under open-circuit conditions at 85°C for >1500 hours.
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The open-circuit voltage (VOC) deficit in perovskite solar cells is greater in wide-bandgap (over 1.7 eV) cells than in perovskites of roughly 1.5 eV (refs. 1,2). Quasi-Fermi-level-splitting measurements show VOC-limiting recombination at the electron-transport-layer contact3-5. This, we find, stems from inhomogeneous surface potential and poor perovskite-electron transport layer energetic alignment. Common monoammonium surface treatments fail to address this; as an alternative, we introduce diammonium molecules to modify perovskite surface states and achieve a more uniform spatial distribution of surface potential. Using 1,3-propane diammonium, quasi-Fermi-level splitting increases by 90 meV, enabling 1.79 eV perovskite solar cells with a certified 1.33 V VOC and over 19% power conversion efficiency (PCE). Incorporating this layer into a monolithic all-perovskite tandem, we report a record VOC of 2.19 V (89% of the detailed balance VOC limit) and over 27% PCE (26.3% certified quasi-steady state). These tandems retained more than 86% of their initial PCE after 500 h of operation.
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Electro-optic (EO) modulators provide electrical-to-optical signal conversion relevant to optical communications. Barium titanate (BaTiO3 ) is a promising material system for EO modulation in light of its optical ultrafast nonlinearity, low optical loss, and high refractive index. To enhance further its spontaneous polarization, BaTiO3 can be doped at the Ba and Ti sites; however, doping is often accompanied by ion migration, which diminishes EO performance. Here, donor-acceptor doping and its effect on EO efficiency are investigated, finding that La-doped BaTiO3 achieves an EO coefficient of 42 pm V-1 at 1 kHz, fully twice that of the pristine specimen; however, it is also observed that, with this single-element doping, the EO response falls off rapidly with frequency. From impedance spectroscopy, it is found that frequency-dependent EO is correlated with ion migration. Density functional theory calculations predict that the ion-migration barrier decreases with La3+ doping but can be recovered with further Mn2+ doping, a finding that prompts to prevent ion migration by incorporating Mn2+ into the Ti-site to compensate for the charge imbalance.
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Accompanying with increases in vehicle population and gasoline consumption, gasoline evaporation accounted for an enlarged portion of total volatile organic compound (VOC) emissions in China, raising increasing environmental concerns especially in megacities. In this study, an intensive sampling campaign was performed in a gasoline service station, to reveal emission characteristics, environmental and health impacts of VOCs. It was strikingly found that 24 % of air samples exceeded the national standard of 4 mg/m3 for non-methane hydrocarbons (NMHCs) on the boundary of the station, with the equipment of Stage I and II controls. VOC groups and species profiles showed that alkanes dominated total VOCs. As typical markers of evaporative loss of gasoline, C4-5 species (i-pentane, n-pentane and n-butane) as well as methyl tert-butyl ether (MTBE) accounted for 49.6 % of VOCs. Species profile and diagnostic ratios indicated the prominent contribution of gasoline evaporative losses from refueling or breathing processes, as well as the interference of vehicle exhaust in the ambient air at the site. Intensive O3 production was reproduced by the photochemical box model, demonstrating that O3 formation was co-limited by both VOCs (especially trans-2-butene) and NOx. Inhalation health risk assessment proved that exposure to hazardous VOCs caused non-cancer risk (HQ = 3.08) and definitely posed cancer risks at a probability of 1.3 × 10-4 to workers. Remarkable health risks were mainly imposed by halocarbons, aromatics and alkenes, in which 1,2-dichloropropane caused the highest non-cancer risk (HQ = 1.3) and acted as the primary carcinogen (ICR = 5.1 × 10-5). This study elucidated the high unqualified rate in gasoline service stations after the implementation of latest standards in China, where new regulations targeted halocarbons and updates in existing vapor recovery systems were suggested for VOC mitigation.
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Contaminantes Atmosféricos , Ozono , Compuestos Orgánicos Volátiles , Contaminantes Atmosféricos/análisis , China , Monitoreo del Ambiente , Gasolina/análisis , Humanos , Ozono/análisis , Fotoquímica , Emisiones de Vehículos/análisis , Compuestos Orgánicos Volátiles/análisisRESUMEN
Continuous measurements of ozone (O3) and nitrogen oxides (NOx = NO + NO2) were conducted from 2007 to 2019 in Hong Kong in order to evaluate the effectiveness of control strategies for NOx emission from diesel commercial vehicles (DCV). DCV control programs were periodically applied in three phases starting from 2007, 2010 and 2014. It was found that NO and NO2 levels decreased during the study period but more dramatically after the implementation of DCV Phase III than pre-DCV Phase III. Source apportionment analysis confirmed that the ambient NO and NO2 in Hong Kong attributed to the regulated DCV emissions in Phase III reduced at rates of 5.1-14.4 ppbv/yr in roadside environment and 1.6-3.1 ppbv/yr in suburban area. Despite overall NOx reduction, increased NO2/NOx ratios were recorded during the study period possibly due to the application of diesel particulate filter (DPF) in DCVs. However, after introducing DCV Phase III, observed O3 values experienced more dramatic increasing trends in most areas of Hong Kong than pre-DCV Phase III. Model simulations revealed that O3 production rate kept increasing and turned to be less sensitive to NOx from 2014 to 2019. On the roadside, net O3 production rate was more than doubled during 2014-2019 owing to NOx reduction. Moreover, the levels of oxidants (OH, HO2 and RO2) were 1.5-5 times those before 2014. In suburban environment, NOx reduction also facilitated O3 production and radical cycling, but made smaller contributions than those on the roadside during 2014-2019. This study unraveled that NOx reductions benefited from DCV regulations caused increase in surface O3 and fueled O3 photochemistry in various environments. More stringent control measures on emissions of VOCs, especially those with high OH reactivity, might help to better mitigate O3 pollution.
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Contaminantes Atmosféricos , Contaminación del Aire , Ozono , Compuestos Orgánicos Volátiles , Contaminantes Atmosféricos/análisis , Contaminación del Aire/análisis , Contaminación del Aire/prevención & control , China , Monitoreo del Ambiente , Hong Kong , Dióxido de Nitrógeno/análisis , Ozono/análisis , Compuestos Orgánicos Volátiles/análisisRESUMEN
We present the continuously measurements of volatile organic compounds (VOCs) at a receptor site (Wan Qing Sha, WQS) in the Pearl River Delta (PRD) region from September to November of 2017. The average mixing ratios of total VOCs (TVOCs) was 36.3 ± 27.9 ppbv with the dominant contribution from alkanes (55.5%), followed by aromatics (33.3%). The diurnal variation of TVOCs showed a strong photochemical consumption during daytime, resulting in the formation of ozone (O3). Five VOC sources were resolved by the positive matrix factorization (PMF) model, including solvent usage (28.6%), liquid petroleum gas (LPG) usage (24.4%), vehicle exhaust (21.0%), industrial emissions (13.2%) and gasoline evaporation (12.9%). The regional transport air masses from the upwind cities of south China can result in the elevated concentrations of TVOCs. Low ratios of TVOCs/NOx (1.53 ± 0.88) suggested that the O3 formation regime at WQS site was VOC-limited, which also confirmed by a photochemical box model with the master chemical mechanism (PBM-MCM). Furthermore, the observation on high-O3 episode days revealed that frequent O3 outbreaks at WQS were mainly caused by the regional transport of anthropogenic VOCs especially for aromatics and the subsequent photochemical reactions. This study provides valuable information for policymakers to propose the effective control strategies on photochemical pollution in a regional perspective.
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Contaminantes Atmosféricos , Ozono , Compuestos Orgánicos Volátiles , Contaminantes Atmosféricos/análisis , China , Monitoreo del Ambiente , Ozono/análisis , Emisiones de Vehículos/análisis , Compuestos Orgánicos Volátiles/análisisRESUMEN
To investigate photochemical ozone (O3) pollution in urban areas in China, O3 and its precursors and meteorological parameters were simultaneously measured in five megacities in China in summer 2018. Moderate wind speeds, strong solar radiation and high temperature were observed in all cities, indicating favorable meteorological conditions for local O3 formation. However, the unusually frequent precipitation caused by typhoons reaching the eastern coastline resulted in the least severe air pollution in Shanghai. The highest O3 level was found in Beijing, followed by Lanzhou and Wuhan, while relatively lower O3 value was recorded in Chengdu and Shanghai. Photochemical box model simulations revealed that net O3 production rate in Lanzhou was the largest, followed by Beijing, Wuhan and Chengdu, while it was the lowest in Shanghai. Besides, the O3 formation was mainly controlled by volatile organic compounds (VOCs) in most cities, but co-limited by VOCs and nitrogen oxides in Lanzhou. Moreover, the dominant VOC groups contributing to O3 formation were oxygenated VOCs (OVOCs) in Beijing and Wuhan, alkenes in Lanzhou, and aromatics and OVOCs in Shanghai and Chengdu. Source apportionment analysis identified six sources of O3 precursors in these cities, including liquefied petroleum gas usage, diesel exhaust, gasoline exhaust, industrial emissions, solvent usage, and biogenic emissions. Gasoline exhaust dominated the O3 formation in Beijing, and LPG usage and industrial emissions made comparable contributions in Lanzhou, while LPG usage and solvent usage played a leading role in Wuhan and Chengdu, respectively. The findings are helpful to mitigate O3 pollution in China.
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Contaminantes Atmosféricos , Ozono , Compuestos Orgánicos Volátiles , Contaminantes Atmosféricos/análisis , China , Ciudades , Monitoreo del Ambiente , Ozono/análisis , Compuestos Orgánicos Volátiles/análisisRESUMEN
Investigating the long-term trends of alkyl nitrates (RONO2) is of great importance for evaluating the variations of photochemical pollution. Mixing ratios of C1-C5 RONO2 were measured in autumn Hong Kong from 2002 to 2016, and the average level of 2-butyl nitrate (2-BuONO2) always ranked first. The C1-C4 RONO2 all showed increasing trends (p < 0.05), and 2-BuONO2 had the largest increase rate. The enhancement in C3 RONO2 was partially related to elevated propane, and dramatic decreases (p < 0.05) in both nitrogen monoxide (NO) and nitrogen dioxide (NO2) also led to the increased RONO2 formation. In addition, an increase of hydroxyl (OH) and hydroperoxyl (HO2) radicals (p < 0.05) suggested enhanced atmospheric oxidative capacity, further resulting in the increases of RONO2. Source apportionment of C1-C4 RONO2 specified three typical sources of RONO2, including biomass burning emission, oceanic emission, and secondary formation, of which secondary formation was the largest contributor to ambient RONO2 levels. Mixing ratios of total RONO2 from each source were quantified and their temporal variations were investigated. Elevated RONO2 from secondary formation and biomass burning emission were two likely causes of increased ambient RONO2. By looking into the spatial distributions of C1-C5 RONO2, regional transport from the Pearl River Delta (PRD) was inferred to build up RONO2 levels in Hong Kong, especially in the northwestern part. In addition, more serious RONO2 pollution was found in western PRD region. This study helps build a comprehensive understanding of RONO2 pollution in Hong Kong and even the entire PRD.
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Contaminantes Atmosféricos , Nitratos , Contaminantes Atmosféricos/análisis , Monitoreo del Ambiente , Hong Kong , Nitratos/análisis , Océanos y MaresRESUMEN
Peroxyacetyl nitrate (PAN) is an important reservoir of atmospheric nitrogen, modulating reactive nitrogen cycle and ozone (O3) formation. To understand the origins of PAN, a field measurement was conducted at Tung Chung site (TC) in suburban Hong Kong from October to November 2016. The average level of PAN was 0.63⯱â¯0.05â¯ppbv, with a maximum of 7.30â¯ppbv. Higher PAN/O3 ratio (0.043-0.058) was captured on episodes, i.e. when hourly maximum O3 exceeded 80â¯ppbv, than on non-episodes (0.01), since O3 production was less efficient than PAN when there was an elevation of precursors (i.e. volatile organic compounds (VOCs) and nitrogen oxide (NOx)). Model simulations revealed that oxidations of acetaldehyde (65.3⯱â¯2.3%), methylglyoxal (MGLY, 12.7⯱â¯1.2%) and other oxygenated VOCs (OVOCs) (8.0⯱â¯0.6%), and radical cycling (12.2⯱â¯0.8%) were the major production pathways of peroxyacetyl (PA) radical, while local PAN formation was controlled by both VOCs and nitrogen dioxide (NO2). Among all VOC species, carbonyls made the highest contribution (59%) to PAN formation, followed by aromatics (26%) and biogenic VOCs (BVOCs) (10%) through direct oxidation/decomposition. Besides, active VOCs (i.e. carbonyls, aromatics, BVOCs and alkenes/alkynes) could stimulate hydroxyl (OH) production, thus indirectly facilitating the PAN formation. Apart from primary emissions, carbonyls were also generated from oxidation of first-generation precursors, i.e., hydrocarbons, of which xylenes contributed the most to PAN production. Furthermore, PAN formation suppressed local O3 formation at a rate of 2.84â¯ppbv/ppbv, when NO2, OH and hydroperoxy (HO2) levels decreased and nitrogen monoxide (NO) value enhanced. Namely, O3 was reduced by 2.84â¯ppbv per ppbv PAN formation. Net O3 production rate was weakened (â¼36%) due to PAN photochemistry, so as each individual production and loss pathway. The findings advanced our knowledge of atmospheric PAN and its impact on O3 production.
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Contaminantes Atmosféricos/análisis , Monitoreo del Ambiente , Contaminación Ambiental/análisis , Ozono/análisis , Ácido Peracético/análogos & derivados , Compuestos Orgánicos Volátiles/análisis , Acetaldehído/química , Hong Kong , Hidrocarburos/análisis , Radical Hidroxilo/análisis , Óxidos de Nitrógeno/análisis , Oxidación-Reducción , Ácido Peracético/análisis , Fotoquímica , Piruvaldehído/química , Xilenos/análisisRESUMEN
Alkyl nitrates (RONO2) are important reservoirs of atmospheric nitrogen, regulating nitrogen cycling and ozone (O3) formation. In this study, we found that propane and n-butane were significantly lower at the offshore site (WSI) in Hong Kong ( p < 0.05), whereas C3-C4 RONO2 were comparable to the suburban site (TC) ( p > 0.05). Stronger oxidative capacity at WSI led to more efficient RONO2 formation. Relative incremental reactivity (RIR) was for the first time used to evaluate RONO2-precursor relationships. In contrast to a consistently volatile organic compounds (VOC)-limited regime at TC, RONO2 formation at WSI switched from VOC-limited regime during O3 episodes to VOC and nitrogen oxides (NO x) colimited regime during nonepisodes. Furthermore, unlike the predominant contributions of parent hydrocarbons to C4-C5 RONO2, the production of C1-C3 RONO2 was more sensitive to other VOCs like aromatics and carbonyls, which accounted for â¼40-90% of the productions of C1-C3 alkylperoxy (RO2) and alkoxy radicals (RO) at both sites. This resulted from the decomposition of larger RO2/RO and the change of OH abundance under the photochemistry of other VOCs. This study advanced our understanding of the photochemical formation of RONO2, particularly the relationships between RONO2 and their precursors, which were not confined to the parent hydrocarbons.
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Contaminantes Atmosféricos , Ozono , Compuestos Orgánicos Volátiles , China , Monitoreo del Ambiente , Hong Kong , Nitratos , Procesos FotoquímicosRESUMEN
This study presents the preparation and characterization of a nanoscale Davankov-type hyper-crosslinked-polymer (HCP) as an adsorbent of benzene-ring-containing dyes and organic pollutants. HCP nanoparticles post-crosslinked from a poly(DVB-co-VBC) precursor were synthesized in this study, possessing ultrahigh surface area, hydrophobicity and stability. The as-synthesized Davankov-type HCP exhibited a rapid and selective adsorption ability towards the benzene-ring-containing dyes due to its highly conjugated structure. Besides, for the first time, the prepared HCP nanoparticles were adopted for the adsorption of nonpolar organic pollutants by means of solid-phase microextraction (SPME). Owing to its high hydrophobicity, diverse pore size distribution and highly conjugated structure, a 10 µm HCP coating exhibited excellent adsorption abilities towards benzene-ring-containing polycyclic aromatic hydrocarbons (PAHs) and benzene series compounds (benzene, toluene, ethylbenzene and o-xylene; abbreviated to BTEX) and to highly hydrophobic long-chain n-alkanes. Finally, the HCP-nanoparticles-coated SPME fiber was applied to the simultaneous analysis of five PAHs in environmental water samples and satisfactory recoveries were achieved. The findings could provide a new benchmark for the exploitation of superb HCPs as effective adsorbents for SPME or other adsorption applications.