Search

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.

TiO2-based nanosheet materials with a core–shell structure are expected to be one of the promising photocatalysts for the degradation of organic pollution. It is a challenge to synthesize TiO2 by the desired nucleation and growth process, so most reported TiO2 core–shell photocatalysts are prepared using TiO2 as a core material. Layered double hydroxides (LDHs) are considered ideal platforms to grow TiO2 in situ and further serve as additional components to improve the separation of photogenerated charge carriers. In this work, we report the design and fabrication of anatase TiO2-coated ZnAl-layered double oxide (LDO@TiO2) nanosheets, which involve the in situ growth of TiO2 on ZnAl-LDH followed by subsequent calcination treatment. The resulting LDO@TiO2 photocatalyst yields typical core–shell nanosheet morphology with a mesoporous structure, exhibiting excellent photodegradation and mineralization efficiency for organic pollution.

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.

Rapid urbanization and industrialization have led to deterioration of air quality in the Beijing–Tianjin–Hebei (BTH) region due to high loadings of PM2.5. Heavy aerosol pollution frequently occurs in winter, in close relation to the planetary boundary layer (PBL) meteorology. To unravel the physical processes that influence PBL structure and aerosol pollution in BTH, this study combined long-term observational data analyses, synoptic pattern classification, and meteorology–chemistry coupled simulations. During the winter of 2017 and 2018, Beijing and Tangshan often experienced heavy PM2.5 pollution simultaneously, accompanied by strong thermal inversion aloft. These concurrences of pollution in different cities were primarily regulated by the large-scale synoptic conditions. Using principal component analysis with geopotential height fields at the 850 hPa level during winter, two typical synoptic patterns associated with heavy pollution in BTH were identified. One pattern is characterized by a southeast-to-north pressure gradient across BTH, and the other is associated with high pressure in eastern China. Both synoptic types feature warmer air temperature at 1000 m a.g.l., which could suppress the development of the PBL. Under these unfavorable synoptic conditions, aerosols can modulate PBL structure through the radiative effect, which was examined using numerical simulations. The aerosol radiative effect can significantly lower the daytime boundary layer height through cooling the surface layer and heating the upper part of the PBL, leading to the deterioration of air quality. This PBL–aerosol feedback is sensitive to the aerosol vertical structure, which is more effective when the synoptic pattern can distribute more aerosols to the upper PBL.

Consensus has been reached that precipitation extremes vary proportionally with global warming. Nevertheless, the underlying cause and magnitude of these factors affecting their relationships remain highly debated. To elucidate the complex relationship between precipitation extremes and temperature in China during the warm seasons (May through September), a 60-year (1958–2017) record of hourly rain gauge measurements, in combination with surface air temperature, RH, precipitable water (PW), and convective available potential energy (CAPE) collected from 120 radiosonde stations were examined. Spatially, the scaling relationship between precipitation extremes and temperature exhibits a large geographic difference across China. In particular, the Clausius–Clapeyron (CC) and sub-CC relationships tend to occur in northwest (ROI-N) and southeast China (ROI-S), whereas the super-CC relationship is found to mainly concentrates in central China (ROI-C). Additionally, the response of precipitation extremes to temperature becomes more sensitive as precipitation intensity increases, shifting from CC to super-CC at a certain point of inflection that varies by geographic regions. This shift occurs at approximately 15 °C in ROI-C and ROI-N, but at around 20 °C in ROI-S. Within the temperature range of the super-CC slope, the PW rises with the increases in temperature, whereas the CAPE decreases with rising temperature, which is contrary to the monotonic scaling of precipitation with temperature. From the perspective of interannual variation, the precipitation extremes correlate positively with temperature. This further confirms the notion that global warming, through jointly affecting PW and CAPE, is able to considerably regulate precipitation extremes.

TiO

To identify potential sources of fine particles (PM

TiO2-based nanosheets materials with core-shell structure are expected to be one of the promising photocatalysts to degradation of organic pollutions. However, it is a challenge to synthesis of TiO2 shell on functional core materials by desired nucleation and growth process. Layered double hydroxides (LDHs) are considered as ideal platforms to in-situ grow TiO2 and further serve as additional components to construct heterojunction to improve the separation of photo-generated charge carriers. In this work, we report the design and fabrication of anatase TiO2 coated ZnAl-layered double oxide (LDO@TiO2) nanosheets, which involves the in-situ growth of TiO2 on ZnAl-LDH followed by a subsequent calcination treatment. The resulting LDO@TiO2 photocatalyst gives typical core-shell nanosheets morphology with mesoporous structure, which exhibiting excellent photodegradation and mineralization efficiency for organic pollutions.

Daily exposure to high ambient PM2.5 increases the mortality rate and contributes significantly to the burden of disease. In basin-situated cities with high local emissions of air pollutants, meteorological conditions play a crucial role in forming air pollution. One such city is Chengdu, which is located in the Sichuan Basin and serves as the economic, educational, and transportation hub of western China. Particulate matter with an aerodynamic diameter of 75 µg m–3. To better understand the influence of meteorological factors on PM2.5 pollution with the goal of easily and reliably predicting the latter, we examined the relationships between the 24-h concentration and a variety of meteorological parameters in Chengdu. We found that the strongest predictors of the PM2.5 concentration were the temperature, precipitation, wind speed, and trajectory direction and distance. Furthermore, although the same-day sea-level pressure (SLP) was a weak predictor, the SLP 5 days in advance performed better. We developed generalized additive models (GAMs) that predicted the PM2.5 concentration as a function of multiple meteorological parameters. One of the GAMs developed in this study exhibited an adjusted correlation coefficient (R2) of 0.73 and captured up to 73.9% of the variance in the daily averaged PM2.5 concentrations. The model performance was improved by using the ΔSLP (i.e., mean pressure difference) for 5 days instead of the SLP, suggesting that ΔSLP5d is a good predictor of high concentration days in Chengdu. This study provides a useful tool for controlling emissions in advance to prevent heavy pollution days and issuing outdoor activity warnings to protect public health.

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.

Purpose of ReviewDuring the past decades, the number and size of megacities have been growing dramatically in China. Most of Chinese megacities are suffering from heavy PM2.5pollution. In the pollution formation, the planetary boundary layer (PBL) plays an important role. This review is aimed at presenting the current state of understanding of the PBL-PM2.5interaction in megacities, as well as to identify the main gaps in current knowledge and further research needs.Recent FindingsThe PBL is critical to the formation of urban PM2.5pollution at multiple temporal scales, ranging from diurnal change to seasonal variation. For the essential PBL structure/process in pollution, the coastal megacities have different concerns from the mountainous or land-locked megacities. In the coastal cities, the recirculation induced by sea-land breeze can accumulate pollutants, whereas in the valley/basin, the blocking effects of terrains can lead to stagnant conditions and thermal inversion. Within a megacity, although the urbanization-induced land use change can cause thermodynamic perturbations and facilitate the development of PBL, the increases in emissions outweigh this impact, resulting in a net increase of aerosol concentration. Moreover, the aerosol radiative effects can modify the PBL by heating the upper layers and reducing the surface heat flux, suppressing the PBL and exacerbating the pollution.SummaryThis review presented the PBL-PM2.5interaction in 13 Chinese megacities with various geographic conditions and elucidated the critical influencing processes. To further understand the complicated interactions, long-term observations of meteorology and aerosol properties with multi-layers in the PBL need to be implemented.

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.

The observed relationships between boundary layer height (BLH) and PM2.5 on a national scale remain unclear due to the dearth of observations. Here we investigated this relationship from a unique perspective of thermodynamic stability in the planetary boundary layer (PBL), using summertime (June–August) soundings from China for the period from 2014 to 2017. For all three times of soundings (0800, 1400, and 2000 Beijing time [BJT]), positive (negative) PM2.5 concentrations anomalies were found to correlate with negative (positive) BLHs anomalies relative to daily means. The negative correlation was strongest at 1400 BJT, followed by 2000 BJT and 0800 BJT. Overall, the PM2.5 was found to nonuniformly anticorrelate with BLH across China at 0800 and 2000 BJT. The strongest anticorrelation occurred in the North China Plain at 1400 BJT, in sharp contrast to the much weaker correlation in other regions characterized by much less polluted regions. The averaged PM2.5 in neutral boundary layers was higher than that in convective boundary layers (CBLs). The CBL, where the anticorrelation was the strongest, was conducive to dissipating more aerosol in the heavily polluted area in China than neutral boundary layer. The higher CBL formed under low cloud cover, low surface humidity, and strong wind speed was favorable for the dispersion of aerosol, in contrast to the stable boundary layers that happen under the highest cloud cover. Also, positive correlation was seen between stable boundary layer and PM2.5. The findings call for attention that the thermodynamical condition of PBL should be considered when examining the aerosol‐PBL interactions.

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.

The rapid development in the economy during past decades has caused serious air pollution issues in China with high concentrations of PM

NH

To elucidate the critical factors influencing the ammonia (NH3) concentration in Beijing, this study combined observational analyses, backward trajectory calculations, and meteorology&ndash, chemistry coupled simulations to investigate the variations in the NH3 concentration from 11 May to 24 June, 2015. A significant positive correlation was found between the NH3 and PM2.5 concentrations in Beijing. By examining the relationships between meteorological parameters and the NH3 concentration, both near-surface temperature and relative humidity showed positive correlations with the NH3 concentration. The higher NH3 concentrations were usually associated with the warming of the upper atmosphere. Distinct wind directions were noted during the days of the top and bottom 33.3% NH3 concentrations. The top 33.3% concentrations were primarily related to southwesterly winds, while the bottom ones were associated with westerly and northerly winds. Since there are strong NH3 emissions in the southern plains adjacent to Beijing, the regional transport induced by the southerly prevailing winds would increase the NH3 concentration in Beijing significantly. From 23 to 25 May, more than one third of NH3 in Beijing was contributed by the southerly transport processes. Thus, joint efforts to reduce NH3 emissions in the whole Beijing&ndash, Tianjin&ndash, Hebei region are necessary to regulate the NH3 concentration in Beijing.

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.

The decreases in diurnal temperature range (DTR) observed in most regions are generally linked to the increase in cloud cover. However, declining clouds and rising aerosols observed over the North China Plain (NCP) of China make it elusive to elucidate the underlying mechanisms behind the declining DTR observed in this region. Here, we analyze the changes in DTR characteristics in the NCP based on 54-year surface temperature observations, in combination with collocated environmental variable measurements. Overall, there is a significant declining trend of DTR from 1960 to 2014 at a rate of − 0.12 °C/decade, largely due to a larger increase in minimum temperature during the night. The cloud effect on DTR is further explored by comparing DTR under clear-sky and overcast conditions, which exhibits a distinct annual cycle with a minimum in summer and a maximum in winter. The decreasing rate of DTR under overcast condition is − 0.30 °C/decade, much faster than the rate of − 0.17 °C/decade under clear-sky condition, indicating steady increases in the nighttime warming effect of middle- or high-clouds. Also, the elevated aerosol concentration could contribute to the declining DTR, due to the cooling effect of aerosols. Moreover, the effect induced by sunshine duration and water vapor on DTR cannot be ignored either. All of the aforementioned environmental variables combine to affect the long-term trend of DTR, despite their different roles in modulating DTR. Our findings call for better understanding of the influence of environmental factors on regional climate system at the diurnal timescale.

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.