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Photoelectrochemical (PEC) water splitting is a promising approach for renewable hydrogen production. However, the practical PEC solar-to-fuel conversion efficiency is still low owing to poor light absorption and rapid recombination of charge carriers in photoelectrode. In this work, we report a ternary photoanode with simultaneously enhancement of light absorption and water oxidation efficiency by introducing copper phthalocyanine (CuPc) and nickel iron-layered double hydroxide (NiFe-LDH) on TiO2 (denoted as TiO2/CuPc/NiFe-LDH). An experimental study reveals that CuPc loading on TiO2 bring strong visible light absorption; NiFe-LDH as an oxygen evolution reaction catalyst efficiently accelerates the surface water oxidation reaction. This synergistic effect of CuPc and NiFe-LDH gives enhanced photocurrent density (2.10 mA/cm2 at 0.6 V vs. SCE) and excellent stability in the ternary TiO2/CuPc/NiFe-LDH photoanode.

CuZr-based alloys are being considered as potential shape memory alloys for use in high-temperature applications. We have conducted a study on the effects of several alloying elements on the shape memory properties of these alloys using polycrystalline thin-film samples. Here we report on the explosive formation of martensite in supercooled CuZr, CuZrNi and CuZrCo samples. This explosive transformation behavior is characterized by the following observations: 1) The high-temperature austenitic phase can be supercooled below the martensite finish temperature Mf. At a critical temperature below Mf, austenite transforms to martensite across the entire sample in less than a microsecond. 2) The critical temperature has a narrow distribution and decreases slightly with higher cooling rate. 3) Observation of supercooling and explosive transformation behavior depends on the temperature history above the austenite finish temperature Af. If a sample is quenched immediately after heating above Af, martensite forms gradually on cooling below Ms; if a sample is allowed to dwell a few seconds above Af, the martensite forms explosively. We suggest that the gradual transformation proceeds by martensite growth on defects that accumulate during successive transformation cycles. If the sample is allowed to dwell at a temperature above Af, however, these defects are annihilated and the transformation is nucleation-limited. Nucleation of martensite then requires significant supercooling. The defect annihilation process is highly sensitive to temperature and has an apparent activation energy of 326 kJ/mol, which is too large for a simple diffusion-limited process. Transmission electron microscopy of CuZrCo samples suggests that the defects may be related to the presence of residual martensite.

We present a computational-experimental study on the ternary alloying effect of CuZr-based shape memory alloy. The transformation behavior, including crystallization, martensite-austenite transformation temperature and hysteresis of Cu-Zr-X (X = Ni, Co, Hf) thin-film samples were investigated by nanocalorimetry. We used ab initio simulations to determine the B2-Cm transformation pathway, evaluate the lattice parameters, the relative phase stability, and the twin boundary energy as a function of composition. Experimental results show that alloying with Ni or Co reduces the hysteresis of the martensitic transformation, while Hf increases it. These observations are in agreement with the trend of the middle eigenvalue of the martensitic transformation matrix. The energy difference between the pure phases obtained from simulations suggests that both Co and Ni stabilize martensite against austenite. However, experiments show that Co decreases transformation temperature, while Ni increases it. We attribute this observation to the larger twin boundary energy and strain energy in the Co-containing alloy. Our results indicate that ab initio simulations are a helpful tool in the development of new shape memory alloys, provided the energy terms associated with the fine twin structure of the martensite are taken into account.

To identify potential sources of fine particles (PM

The day-to-day variations in the planetary boundary layer (PBL) structure and air quality are closely governed by large-scale synoptic forcings. Partly due to the lack of long-term PBL observations during the winter in Beijing, the complex relationships between the large-scale synoptic patterns, local PBL structures/processes, and PM2.5 pollution have not been fully understood. Thus, this study systematically investigated these linkages by combining aerosol measurements, surface meteorological observations, radiosonde data, reanalysis, long-term three-dimensional meteorological simulations, and idealized meteorology-chemistry coupled simulations. Based on the validated long-term simulation results, the boundary layer height (BLH) in Beijing during two winters from 2013 to 2015 was calculated and compared with PM2.5 measurements. A significant anti-correlation was found between the daily BLH and PM2.5 concentration in Beijing, indicating the importance of the PBL structure on the variations in the aerosol pollution levels. Those days with low BLHs are often accompanied by a strong elevated thermal inversion layer. Based on the daily 900-hPa geopotential height fields, seven synoptic patterns were identified using an objective approach, in which two types were found to be associated with heavy PM2.5 pollution in Beijing. One pattern was characterized by weak northwesterly prevailing winds and a strong elevated thermal inversion layer over Beijing, and the local emissions of aerosols played a decisive role in the formation of heavy pollution. The other pattern was associated with southerly prevailing winds, which could transport the pollutants emitted from southern cities to Beijing. According to the meteorology-chemistry coupled simulations, southerly regional transportation can contribute approximately 56% of the PM2.5 in Beijing. The results of this study have important implications for understanding the crucial roles that multiscale meteorological factors play in modulating the aerosol pollution in Beijing during the winter.

We have developed sensor arrays using a simple and inexpensive fabrication process to measure the electrical resistance of thin-film materials as a function of temperature and composition. The sensors are capable of characterizing materials from liquid‑nitrogen temperature to approximately 900 K and are not limited by low sample conductivity. We demonstrate the sensitivity and accuracy of the technique by analyzing the phase evolution in Ti-Ni-Cu shape memory alloys and PdSi-based metallic glasses. For the latter, we find that the change in resistance on crystallization correlates with glass-forming ability. This observation may be useful in identifying good glass formers using high-throughput techniques.

China suffers from high levels of PM2.5 pollution, which is often exacerbated by unfavorable planetary boundary layer (PBL) structures. Partly due to a lack of appropriate observations, the PBL-aerosol linkages in China are not clearly understood. Thus, we investigated these linkages from a national perspective using sounding data collected from 2014 to 2017. Correlation analyses revealed a significant anti-correlation between monthly boundary layer height (BLH) and aerosol pollution that was ubiquitous across China, indicating the important role of the PBL in regulating the seasonal variations of pollution in China. Besides, the day-to-day variations in pollution were modulated by the daily variabilities in the PBL structure. During winter, highly polluted days in most of the Chinese cities studied were associated with a low BLH, strong thermal stability, and weak PBL winds. In the North China Plain and Northeast China, the wintertime heavy pollution was often related to southerly winds and moister PBL. This study has important implications for understanding the crucial role that the PBL plays in modulating aerosol pollution in China.

Monoclinic bismuth vanadate (BiVO4) shows promising application prospect in photoelectrochemical (PEC) water splitting on account of its relatively ideal band gap to harvest sunlight. However, the poor charge migrate property and sluggish water oxidation kinetics severely limit the PEC performance of BiVO4 photoelectrodes. In this work, BiVO4 photoanode with highly exposed (040) facets for superior charge transfer was prepared by a seed assisted hydrothermal method. Moreover, cobalt single atoms stabilized in N-doped carbon nanosheet (Co SAs-NC) was well modified on BiVO4 (040) (denoted as BiVO4 (040)/Co SAs-NC) with much improved water oxidation efficiency. The as-prepared BiVO4 (040)/Co SAs-NC photoanode generated 2.2 times higher photocurrent density than that of pristine BiVO4 (040) at 1.23 V vs. RHE, and presented nearly 100% charge injection efficiency. The detail kinetic measurements reveal that the modified Co SAs-NC cocatalyst effectively suppresses the carrier recombination and promotes the surface reaction kinetics. This work provides a promising strategy to fabricate composite photoanodes for solar energy conversion based on facet engineering matched with single-atomic-catalyst.

Most cities in China experience frequent PM2.5 pollution, in relation to unfavorable planetary boundary layer (PBL) conditions. Partly due to the limited appropriate PBL observations, the explicit relationships between PBL structure/process and PM2.5 pollution in China are not yet clearly understood. Using the fine-resolution sounding measurements from 2014 to 2017, the relationships between boundary layer height (BLH) and PM2.5 pollution in China were systematically examined. Four regions of interest (ROIs) featured with dense population and heavy pollution were studied and compared, including Northeast China (NEC), North China Plain (NCP), East China (EC), and Sichuan Basin (SCB). From 2014 to 2017, the heaviest PM2.5 pollution happened in NCP with an annual average concentration of 84 μg m−3, followed by NEC (60 μg m−3), SCB (57 μg m−3), and EC (54 μg m−3). Correlation analyses revealed a significant anti-correlation between BLH and daily PM2.5 concentrations across China, independent of ROIs. During an annual cycle, the pollution was heaviest in winter, followed by fall and spring, and reached its minimum in summer. Such a seasonal variation of pollution was not only modulated by the emissions, but also the seasonal shifts of BLH. The low BLH in winter was often associated with strong near-surface thermal stability. Moreover, certain synoptic conditions in winter can exacerbate the pollution, leading to concurrent drops of BLH and synchronous increases of PM2.5 concentration in different cities of a ROI. In NCP and SCB, the mountainous terrains could further worsen the pollution by blocking effects and lee eddies.

We have investigated the phase transformations in sputtered CuZr shape memory thin films using a differential nanocalorimetry technique that is capable of making calorimetric measurement on thin-film samples with a sensitivity as small as 12 pJ/K. We first present a general procedure to accurately measure the heat capacity and enthalpies of transformation of a sample, even if there is a significant difference in the heat capacities of sample and reference. We then demonstrate the technique by analyzing the phase evolution of equiatomic CuZr thin films and explore the conditions for the formation of the martensitic phase responsible for the shape memory properties of this alloy. We show that fast, low-temperature cycling through the martensitic transformation increases the hysteresis, which we attribute to the accumulation of defects during the martensitic transformation. If the austenitic phase is given sufficient time at elevated temperature to annihilate these defects, the transformation is stable under thermal cycling conditions.

We describe a sensor for measuring the electrical resistance of a conducting thin-film material as a function of temperature and composition. The sensor has excellent sensitivity and can be used at temperatures as high as the melting temperature of the material of interest. The sensor is fabricated by applying a simple lift-off process to a thin film. By combining combinatorial sputtering to fabricate composition spreads with arrays of sensors, the phase transformation behavior of complex alloys can be mapped. We demonstrate this capabilities by using the sensor to determine the glass transition and crystallization temperatures of several PdSiCu-based metallic glasses. We found that in two glass-forming systems, PdCuSi and NiZr, the ratio of the resistance of the crystallized to as-deposited material is correlated with the glass-forming ability. The ability to readily determine glass forming ability, suggests that the sensor is a powerful tool for measuring the glass-forming ability in a high-throughput manner over large compositional spaces.

The northeastern China frequently experiences severe aerosol pollution in winter under unfavorable meteorological conditions. How and to what extent the meteorological factors affect the air quality there are not yet clearly understood. Thus, this study investigated the impacts of synoptic patterns on the aerosol transport and planetary boundary layer (PBL) structure in Shenyang from 1 to 3 December 2016, using surface observations, sounding measurements, satellite data, and three-dimensional simulations. Results showed that the aerosol pollution occurred in Shenyang was not only related to the local emissions, but also contributed by trans-boundary transport of aerosols from the Beiijng-Tianjin-Hebei (BTH) region. In the presence of the westerly and southwesterly synoptic winds, the aerosols emitted from BTH could be brought to Shenyang. From December 2 to 3, the aerosols emitted from BTH accounted for ∼20% of near-surface PM2.5 in Shenyang. In addition, the large-scale synoptic forcings could affect the vertical mixing of pollutants through modulating the PBL structure in Shenyang. The westerly and southwesterly synoptic winds not only brought the aerosols but also the warmer air masses from the southwest regions to Shenyang. The strong warm advections above PBL could enhance the already existing thermal inversion layers capping over PBL in Shenyang, leading to the suppressions of PBL. Both the trans-boundary transport of aerosols and the suppressions of PBL caused by the large-scale synoptic forcings should be partly responsible for the poor air quality in Shenyang, in addition to the high pollutant emissions. The present study revealed the physical mechanisms underlying the aerosol pollution in Shenyang, which has important implications for better forecasting and controlling the aerosols pollution.

Northeast China frequently experiences aerosol pollution episodes in winter. In addition to the pollutant emissions, synoptic pattern and topography can impact the air quality in complex ways, which are still not well understood in Northeast China. Therefore, the impacts of synoptic forcing and topography on aerosol pollution in Shenyang were investigated combining surface observations, sounding measurements, and three-dimensional air quality simulations. The studied pollution episode occurred from January 1 to 5, 2020, along with poor meteorological dispersion conditions characterized by weak winds, strong thermal stabilities, and shallow planetary boundary layers (PBLs). During the formation of pollution, strong elevated thermal inversion layers were observed over Shenyang, induced by the large-scale synoptic pattern, which suppressed the PBL growth and the vertical dispersion of aerosols. Moreover, the blocking effect of mountains to the east of Shenyang further worsened the pollution when northwesterly/westerly flows prevailed in shallow PBLs. Numerical sensitive experiment was conducted to estimate the contribution of blocking effect of mountains to the near-surface PM2.5 concentration in Shenyang, and it was found that around one third of PM2.5 concentration during January 1–4 was relevant to the terrain effect. These findings can facilitate a comprehensive understanding of the physical formation of aerosol pollution in Northeast China and helpful for the pollution controls.

Partly due to the lack of fine-resolution measurements of the planetary boundary layer (PBL), the impacts of PBL on the aerosol pollution in the densely populous Shandong province were not well understood. On the basis of long-term PM2.5 measurements, fine-resolution radiosonde data, and meteorological reanalysis from April 2016 to March 2019, the aerosol pollution in Jinan and Qingdao and its complex relationships with the multi-scale meteorological conditions were investigated in this study. During an annual cycle, prominent seasonal variations of PM2.5 concentrations can be observed in both cities, with heaviest pollution in the heating season and relatively low concentrations in summer. Significant positive correlationwas found between the monthly PM2.5 concentrations and thermal stability of the lower troposphere, indicating that the seasonal shifts of PBL play an important role in regulating the variations of aerosol pollution, in addition to the seasonal changes in the emissions. In the heating season, influenced by unfavorable synoptic patterns, heavy pollution often simultaneously happened in Jinan and Qingdao. Utilizing an objective synoptic classification approach with reanalysis data, two dominant synoptic types led to heavy pollution in Jinan and Qingdao were identified, which were featured by 900-hPa warm advections from the west or southwest with weaker prevailing winds. These synoptic types not only strengthened the elevated thermal inversion and inhibited the vertical dilution of pollutants locally, but also caused the regional transports of pollutants to Jinan and Qingdao from high-emission upstream regions, such as the Beijing-Tianjin-Hebei region, Henan province and Jiangsu province. Therefore, to prevent heavy pollution in Jinan and Qingdao, regional joint measures should be implemented with full consideration of synoptic impact.

The Beijing-Tianjin-Hebei (BTH) region experiences heavy aerosol pollution, which is found to have close relationships with the synoptic- and local-scale atmospheric circulations. However, how and to what extent these multi-scale circulations interplay to modulate aerosol transport have not been fully understood. To this end, this study comprehensively investigated the impacts of these circulations on aerosol transport in BTH by focusing on an episode occurred on 1 June 2013 through combining both observations and three-dimensional simulations. It was found that during this episode, the Bohai Sea acted as a transfer station, and the high-pressure system over the Yellow Sea and sea-breeze in BTH took turns to affect the transport of aerosols. In the morning, influenced by the high-pressure system, lots of aerosols emitted from Shandong and Jiangsu provinces were first transported to the Bohai Sea. After then, these aerosols were brought to the BTH region in the afternoon through the inland penetration of sea-breeze, significantly exacerbating the air quality in BTH. The inland penetration of sea-breeze could be identified by the sharp changes in ground-based observed temperature, humidity, and wind when the sea-breeze front (SBF) passed by. Combining observations with model outputs, the SBF was found to be able to advance inland more than ∼150 km till reaching Beijing. This study has important implications for better understanding the aerosol transport in BTH, and improving the forecast of such aerosol pollution.

We present a computational-experimental study on the ternary alloying effect of CuZr-based shape memory alloy. The transformation behavior, including crystallization, martensite-austenite transformation temperature and hysteresis of Cu-Zr-X (X = Ni, Co, Hf) thin-film samples were investigated by nanocalorimetry. We used ab initio simulations to determine the B2-Cm transformation pathway, evaluate the lattice parameters, the relative phase stability, and the twin boundary energy as a function of composition. Experimental results show that alloying with Ni or Co reduces the hysteresis of the martensitic transformation, while Hf increases it. These observations are in agreement with the trend of the middle eigenvalue of the martensitic transformation matrix. The energy difference between the pure phases obtained from simulations suggests that both Co and Ni stabilize martensite against austenite. However, experiments show that Co decreases transformation temperature, while Ni increases it. We attribute this observation to the larger twin boundary energy and strain energy in the Co-containing alloy. Our results indicate that ab initio simulations are a helpful tool in the development of new shape memory alloys, provided the energy terms associated with the fine twin structure of the martensite are taken into account.

The rapid development in the economy during past decades has caused serious air pollution issues in China with high concentrations of PM2.5 and O3, particularly in the densely populous cities. To integrate PM2.5 and O3 controls, it is necessary to understand the impacts of meteorology on both pollutants. Thereby, the complex linkages between planetary boundary layer (PBL), synoptic forcing, regional transport, and heavy pollution in Beijing and Shanghai during summer were investigated using long-term measurements, simulations, and reanalysis. Influenced by the unfavorable meteorological conditions, PM2.5 pollution and O3 pollution often simultaneously occurred. In Beijing, the heavy concurring pollutions usually happened on the days with shallow afternoon PBL and southerly/southwesterly prevailing winds. Within the PBL, the pollutants emitted from the southern plains can be transported to Beijing and accumulated on the windward side of the mountains. At the top of PBL, the synoptic southerly warm advections can strengthen the elevated thermal inversion layer and suppress the development of PBL, leading to worse pollution. Contrarily, the heavy pollutions in Shanghai usually occurred on the days with deep afternoon PBL and southwesterly warm advections within the PBL. Although the warm advections were more favorable to the PBL development than the movements of cool marine air mass, the input of pollutants from the southwest can overweigh this advantage, resulting in poor air quality in Shanghai. The occurrence of heavy pollution or clean condition in Shanghai was primarily determined by the synoptic forcing rather than the local PBL structure. This comparative study indicates that the relationship between PBL height and pollution level is changeable and complicated, which needs to be elucidated from the synoptic perspective.

Emission control measures have been implemented to make air quality good enough for Asia-Pacific Economic Cooperation (APEC) China 2014, which provides us with an ideal test-bed to determine how these measures affect air quality in Beijing and surrounding areas. Based on hourly observations at eight monitoring sites of Beijing, the concentrations of other primary atmospheric pollutants during APEC were found to have significantly lower magnitudes than those before APEC, with the exception of a higher O3 concentration. Overall, WRF/Chem reproduced the observed time series of PM2.5, PM10, NO2, CO, and O3 notably well. To investigate the impact of emission control measures on air quality on both local and regional scales, four emission control schemes were developed according to the locations where emission reduction had taken place; the corresponding simulations were subsequently run separately. Scheme S2 (emission control implemented in Beijing) resulted in reductions of 22%, 24%, 10% and 22% for the concentrations of PM2.5, PM10, NO2 and CO, respectively, compared with 14%, 14%, 8%, and 13% for scheme S3 (emission controls implemented from outside of Beijing). This finding indicates that the local emission reduction in Beijing contributes more to the improved air quality in Beijing during APEC China 2014 than does the emission reduction from outside of Beijing. In terms of the impact on the regional scale, the real emission control scheme led to significant reduction of PM2.5 throughout the whole domain. Although the regional impact cannot be completely ignored, both emission reduction measures implemented in Beijing and those implemented outside of Beijing favor greater reduction in PM2.5 in the domains where measurements are presumably taken, as compared with other domains. Therefore, to improve the air quality in Beijing, more coordinated efforts should be made, particularly in the aspect of more stringent reduction and control strategies on pollutant emission sources across the NCP.

Wuhan, one of the most developed cities in Central China, has been experiencing frequent heavy haze pollution. To understand the impacts of large-scale synoptic patterns and the local-scale planetary boundary layer (PBL) structures on the PM2.5 pollution in Wuhan, this study applied an objective approach to the classifying of the daily synoptic patterns in 2017. It then combined observational analyses and meteorology-chemistry coupled simulations to investigate a typical pollution episode at the end of November 2017. The synoptic type associated with the heaviest PM2.5 pollution in Wuhan was characterized by high pressure to the northwest and low pressure to the northeast at the 850-hPa level, which can support northwesterly prevailing winds towards Wuhan. As a result, the aerosols from the highly polluted northern regions can be transported to Wuhan, leading to a high PM2.5 concentration. Also, when there was high pressure located to the east/southeast of Wuhan at the 850-hPa level, southerly warm advections could be induced. The warming of upper air can significantly suppress the development of PBL by enhancing thermal stability, favoring the accumulation of aerosols. This study elucidated the multi-scale physical mechanisms underlying the aerosol pollution in Wuhan, and has important implications for the forecasting and the mitigating of pollution.

The effects of different Planetary Boundary Layer (PBL) structures on pollutant dispersion processes within two idealized street canyon configurations and a realistic urban area were numerically examined by a Computational Fluid Dynamics (CFD) model. The boundary conditions of different PBL structures/conditions were provided by simulations of the Weather Researching and Forecasting model. The simulated results of the idealized 2D and 3D street canyon experiments showed that the increment of PBL instability favored the downward transport of momentum from the upper flow above the roof to the pedestrian level within the street canyon. As a result, the flow and turbulent fields within the street canyon under the more unstable PBL condition are stronger. Therefore, more pollutants within the street canyon would be removed by the stronger advection and turbulent diffusion processes under the unstable PBL condition. On the contrary, more pollutants would be concentrated in the street canyon under the stable PBL condition. In addition, the simulations of the realistic building cluster experiments showed that the density of buildings was a crucial factor determining the dynamic effects of the PBL structure on the flow patterns. The momentum field within a denser building configuration was mostly transported from the upper flow, and was more sensitive to the PBL structures than that of the sparser building configuration. Finally, it was recommended to use the Mellor–Yamada–Nakanishi–Niino (MYNN) PBL scheme, which can explicitly output the needed turbulent variables, to provide the boundary conditions to the CFD simulation.

Dye-sensitized solar cells (DSSCs) were fabricated using double layers of nano-structured TiO2 films as photoanodes. Different anode architectures of double-layered TiO2 films were fabricated in order to study the structural effect of photoanodes on the solar cell efficiency. The performances of DSSCs based on composite photoanodes in the forms of TiO2 nanoparticles/nanobelts (TiO2 P–B), TiO2 nanoparticles/nanoparticles (TiO2 P–P), TiO2 nanobelts/nanobelts (TiO2 B–B) double-layered electrodes with the same film thicknesses were studied in detail, and their corresponding efficiencies were 4.81%, 3.55% and 0.36%. The work shows that significant improvement of efficiency can be achieved through combined enhancement in optical scattering using the TiO2 nanobelts and high dye absorbing capacity of the TiO2 nanoparticles.