Crystal-Phase Engineering in Heterogeneous Catalysis.

The performance of a chemical reaction is critically dependent on the electronic and/or geometric structures of a material in heterogeneous catalysis. Over the past century, the Sabatier principle has already provided a conceptual framework for optimal catalyst design by adjusting the electronic structure of the catalytic material via a change in composition. Beyond composition, it is essential to recognize that the geometric atomic structures of a catalyst, encompassing terraces, edges, steps, kinks, and corners, have a substantial impact on the activity and selectivity of a chemical reaction. Crystal-phase engineering has the capacity to bring about substantial alterations in the electronic and geometric configurations of a catalyst, enabling control over coordination numbers, morphological features, and the arrangement of surface atoms. Modulating the crystallographic phase is therefore an important strategy for improving the stability, activity, and selectivity of catalytic materials. Nonetheless, a complete understanding of how the performance depends on the crystal phase of a catalyst remains elusive, primarily due to the absence of a molecular-level view of active sites across various crystal phases. In this review, we primarily focus on assessing the dependence of catalytic performance on crystal phases to elucidate the challenges and complexities inherent in heterogeneous catalysis, ultimately aiming for improved catalyst design.

Structure Sensitivity of Metal Catalysts Revealed by Interpretable Machine Learning and First-Principles Calculations.

The nature of the active sites and their structure sensitivity are the keys to rational design of efficient catalysts but have been debated for almost one century in heterogeneous catalysis. Though the Brønsted-Evans-Polanyi (BEP) relationship along with linear scaling relation has long been used to study the reactivity, explicit geometry, and composition properties are absent in this relationship, a fact that prevents its exploration in structure sensitivity of supported catalysts. In this work, based on interpretable multitask symbolic regression and a comprehensive first-principles data set, we discovered a structure descriptor, the topological under-coordinated number mediated by number of valence electrons and the lattice constant, to successfully address the structure sensitivity of metal catalysts. The database used for training, testing, and transferability investigation includes bond-breaking barriers of 20 distinct chemical bonds over 10 transition metals, two metal crystallographic phases, and 17 different facets. The resulting 2D descriptor composing the structure term and the reaction energy term shows great accuracy to predict the reaction barriers and generalizability over the data set with diverse chemical bonds in symmetry, bond order, and steric hindrance. The theory is physical and concise, providing a constructive strategy not only to understand the structure sensitivity but also to decipher the entangled geometric and electronic effects of metal catalysts. The insights revealed are valuable for the rational design of the site-specific metal catalysts.

Tungsten-Iron-Ruthenium Ternary Alloy Immobilized into the Inner Nickel Foam for High-Current-Density Water Oxidation.

The pursuit of highly-active and stable catalysts in anodic oxygen evolution reaction (OER) is desirable for high-current-density water electrolysis toward industrial hydrogen production. Herein, a straightforward yet feasible method to prepare WFeRu ternary alloying catalyst on nickel foam is demonstrated, whereby the foreign W, Fe, and Ru metal atoms diffuse into the Ni foam resulting in the formation of inner immobilized ternary alloy. Thanks to the synergistic impact of foreign metal atoms and structural robustness of inner immobilized alloying catalyst, the well-designed WFeRu@NF self-standing anode exhibits superior OER activities. It only requires overpotentials of 245 and 346 mV to attain current densities of 20 and 500 mA cm-2, respectively. Moreover, the as-prepared ternary alloying catalyst also exhibits a long-term stability at a high-current-density of 500 mA cm-2 for over 45 h, evidencing the inner-immobilization strategy is promising for the development of highly active and stable metal-based catalysts for high-density-current water oxidation process.

Constructing Metal(II)-Sulfate Site Catalysts toward Low Overpotential Carbon Dioxide Electroreduction to Fuel Chemicals.

Precise regulation of the active site structure is an important means to enhance the activity and selectivity of catalysts in CO2 electroreduction. Here, we creatively introduce anionic groups, which can not only stabilize metal sites with strong coordination ability but also have rich interactions with protons at active sites to modify the electronic structure and proton transfer process of catalysts. This strategy helps to convert CO2 into fuel chemicals at low overpotentials. As a typical example, a composite catalyst, CuO/Cu-NSO4/CN, with highly dispersed Cu(II)-SO4 sites has been reported, in which CO2 electroreduction to formate occurs at a low overpotential with a high Faradaic efficiency (-0.5 V vs. RHE, FEformate=87.4 %). Pure HCOOH is produced with an energy conversion efficiency of 44.3 % at a cell voltage of 2.8 V. Theoretical modeling demonstrates that sulfate promotes CO2 transformation into a carboxyl intermediate followed by HCOOH generation, whose mechanism is significantly different from that of the traditional process via a formate intermediate for HCOOH production.

Identifying dominant environmental predictors of freshwater wetland methane fluxes across diurnal to seasonal time scales.

While wetlands are the largest natural source of methane (CH4 ) to the atmosphere, they represent a large source of uncertainty in the global CH4 budget due to the complex biogeochemical controls on CH4 dynamics. Here we present, to our knowledge, the first multi-site synthesis of how predictors of CH4 fluxes (FCH4) in freshwater wetlands vary across wetland types at diel, multiday (synoptic), and seasonal time scales. We used several statistical approaches (correlation analysis, generalized additive modeling, mutual information, and random forests) in a wavelet-based multi-resolution framework to assess the importance of environmental predictors, nonlinearities and lags on FCH4 across 23 eddy covariance sites. Seasonally, soil and air temperature were dominant predictors of FCH4 at sites with smaller seasonal variation in water table depth (WTD). In contrast, WTD was the dominant predictor for wetlands with smaller variations in temperature (e.g., seasonal tropical/subtropical wetlands). Changes in seasonal FCH4 lagged fluctuations in WTD by ~17 ± 11 days, and lagged air and soil temperature by median values of 8 ± 16 and 5 ± 15 days, respectively. Temperature and WTD were also dominant predictors at the multiday scale. Atmospheric pressure (PA) was another important multiday scale predictor for peat-dominated sites, with drops in PA coinciding with synchronous releases of CH4 . At the diel scale, synchronous relationships with latent heat flux and vapor pressure deficit suggest that physical processes controlling evaporation and boundary layer mixing exert similar controls on CH4 volatilization, and suggest the influence of pressurized ventilation in aerenchymatous vegetation. In addition, 1- to 4-h lagged relationships with ecosystem photosynthesis indicate recent carbon substrates, such as root exudates, may also control FCH4. By addressing issues of scale, asynchrony, and nonlinearity, this work improves understanding of the predictors and timing of wetland FCH4 that can inform future studies and models, and help constrain wetland CH4 emissions.

Structure Sensitivity of Au-TiO2 Strong Metal-Support Interactions.

Strong metal-support interactions (SMSI) is an important concept in heterogeneous catalysis. Herein, we demonstrate that the Au-TiO2 SMSI of Au/TiO2 catalysts sensitively depends on both Au nanoparticle (NP) sizes and TiO2 facets. Au NPs of ca. 5 nm are more facile undergo Au-TiO2 SMSI than those of ca. 2 nm, while TiO2 {001} and {100} facets are more facile than TiO2 {101} facets. The resulting capsulating TiO2-x overlayers on Au NPs exhibit an average oxidation state between +3 and +4 and a Au-to-TiO2-x charge transfer, which, combined with calculations, determines the Ti:O ratio as ca. 6:11. Both TiO2-x overlayers and TiO2-x -Au interface exhibit easier lattice oxygen activation and higher intrinsic activity in catalyzing low-temperature CO oxidation than the starting Au-TiO2 interface. These results advance fundamental understanding of SMSI and demonstrate engineering of metal NP size and oxide facet as an effective strategy to tune the SMSI for efficient catalysis.

Critical land change information enhances the understanding of carbon balance in the United States.

Large-scale terrestrial carbon (C) estimating studies using methods such as atmospheric inversion, biogeochemical modeling, and field inventories have produced different results. The goal of this study was to integrate fine-scale processes including land use and land cover change into a large-scale ecosystem framework. We analyzed the terrestrial C budget of the conterminous United States from 1971 to 2015 at 1-km resolution using an enhanced dynamic global vegetation model and comprehensive land cover change data. Effects of atmospheric CO2 fertilization, nitrogen deposition, climate, wildland fire, harvest, and land use/land cover change (LUCC) were considered. We estimate annual C losses from cropland harvest, forest clearcut and thinning, fire, and LUCC were 436.8, 117.9, 10.5, and 10.4 TgC/year, respectively. C stored in ecosystems increased from 119,494 to 127,157 TgC between 1971 and 2015, indicating a mean annual net C sink of 170.3 TgC/year. Although ecosystem net primary production increased by approximately 12.3 TgC/year, most of it was offset by increased C loss from harvest and natural disturbance and increased ecosystem respiration related to forest aging. As a result, the strength of the overall ecosystem C sink did not increase over time. Our modeled results indicate the conterminous US C sink was about 30% smaller than previous modeling studies, but converged more closely with inventory data.

Effects of 21st-century climate, land use, and disturbances on ecosystem carbon balance in California.

Terrestrial ecosystems are an important sink for atmospheric carbon dioxide (CO2 ), sequestering ~30% of annual anthropogenic emissions and slowing the rise of atmospheric CO2 . However, the future direction and magnitude of the land sink is highly uncertain. We examined how historical and projected changes in climate, land use, and ecosystem disturbances affect the carbon balance of terrestrial ecosystems in California over the period 2001-2100. We modeled 32 unique scenarios, spanning 4 land use and 2 radiative forcing scenarios as simulated by four global climate models. Between 2001 and 2015, carbon storage in California's terrestrial ecosystems declined by -188.4 Tg C, with a mean annual flux ranging from a source of -89.8 Tg C/year to a sink of 60.1 Tg C/year. The large variability in the magnitude of the state's carbon source/sink was primarily attributable to interannual variability in weather and climate, which affected the rate of carbon uptake in vegetation and the rate of ecosystem respiration. Under nearly all future scenarios, carbon storage in terrestrial ecosystems was projected to decline, with an average loss of -9.4% (-432.3 Tg C) by the year 2100 from current stocks. However, uncertainty in the magnitude of carbon loss was high, with individual scenario projections ranging from -916.2 to 121.2 Tg C and was largely driven by differences in future climate conditions projected by climate models. Moving from a high to a low radiative forcing scenario reduced net ecosystem carbon loss by 21% and when combined with reductions in land-use change (i.e., moving from a high to a low land-use scenario), net carbon losses were reduced by 55% on average. However, reconciling large uncertainties associated with the effect of increasing atmospheric CO2 is needed to better constrain models used to establish baseline conditions from which ecosystem-based climate mitigation strategies can be evaluated.

A Linear Scaling Relation for CO Oxidation on CeO2-Supported Pd.

Resolving the structure and composition of supported nanoparticles under reaction conditions remains a challenge in heterogeneous catalysis. Advanced configurational sampling methods at the density functional theory level are used to identify stable structures of a Pd8 cluster on ceria (CeO2) in the absence and presence of O2. A Monte Carlo method in the Gibbs ensemble predicts Pd-oxide particles to be stable on CeO2 during CO oxidation. Computed potential energy diagrams for CO oxidation reaction cycles are used as input for microkinetics simulations. Pd-oxide exhibits a much higher CO oxidation activity than metallic Pd on CeO2. This work presents for the first time a scaling relation for a CeO2-supported metal nanoparticle catalyst in CO oxidation: a higher oxidation degree of the Pd cluster weakens CO binding and facilitates the rate-determining CO oxidation step with a ceria O atom. Our approach provides a new strategy to model supported nanoparticle catalysts.

Chemical Insights into the Design and Development of Face-Centered Cubic Ruthenium Catalysts for Fischer-Tropsch Synthesis.

Ruthenium is a promising low-temperature catalyst for Fischer-Tropsch synthesis (FTS). However, its scarcity and modest specific activity limit its widespread industrialization. We demonstrate here a strategy for tuning the crystal phase of catalysts to expose denser and active sites for a higher mass-specific activity. Density functional theory calculations show that upon CO dissociation there are a number of open facets with modest barrier available on the face-centered cubic (fcc) Ru but only a few step edges with a lower barrier on conventional hexagonal-closest packed (hcp) Ru. Guided by theoretical calculations, water-dispersible fcc Ru catalysts containing abundant open facets were synthesized and showed an unprecedented mass-specific activity in the aqueous-phase FTS, 37.8 molCO·molRu-1·h-1 at 433 K. The mass-specific activity of the fcc Ru catalysts with an average size of 6.8 nm is about three times larger than the previous best hcp catalyst with a smaller size of 1.9 nm and a higher specific surface area. The origin of the higher mass-specific activity of the fcc Ru catalysts is identified experimentally from the 2 orders of magnitude higher density of the active sites, despite its slightly higher apparent barrier. Experimental results are in excellent agreement with prediction of theory. The great influence of the crystal phases on site distribution and their intrinsic activities revealed here provides a rationale design of catalysts for higher mass-specific activity without decrease of the particle size.

Interannual variation in methane emissions from tropical wetlands triggered by repeated El Niño Southern Oscillation.

Methane (CH4 ) emissions from tropical wetlands contribute 60%-80% of global natural wetland CH4 emissions. Decreased wetland CH4 emissions can act as a negative feedback mechanism for future climate warming and vice versa. The impact of the El Niño-Southern Oscillation (ENSO) on CH4 emissions from wetlands remains poorly quantified at both regional and global scales, and El Niño events are expected to become more severe based on climate models' projections. We use a process-based model of global wetland CH4 emissions to investigate the impacts of the ENSO on CH4 emissions in tropical wetlands for the period from 1950 to 2012. The results show that CH4 emissions from tropical wetlands respond strongly to repeated ENSO events, with negative anomalies occurring during El Niño periods and with positive anomalies occurring during La Niña periods. An approximately 8-month time lag was detected between tropical wetland CH4 emissions and ENSO events, which was caused by the combined time lag effects of ENSO events on precipitation and temperature over tropical wetlands. The ENSO can explain 49% of interannual variations for tropical wetland CH4 emissions. Furthermore, relative to neutral years, changes in temperature have much stronger effects on tropical wetland CH4 emissions than the changes in precipitation during ENSO periods. The occurrence of several El Niño events contributed to a lower decadal mean growth rate in atmospheric CH4 concentrations throughout the 1980s and 1990s and to stable atmospheric CH4 concentrations from 1999 to 2006, resulting in negative feedback to global warming.

Carbon induced selective regulation of cobalt-based Fischer-Tropsch catalysts by ethylene treatment.

Various carbonaceous species were controllably deposited on Co/Al2O3 catalysts using ethylene as carbon source during the activation process for Fischer-Tropsch synthesis (FTS). Atomic, polymeric and graphitic carbon were distinguished by Raman spectroscopy, thermoanalysis and temperature programmed hydrogenation. Significant changes occurred in both the catalytic activity and selectivity toward hydrocarbon products after ethylene treatment. The activity decreased along with an increase in CH4 selectivity, at the expense of a remarkable decrease of heavy hydrocarbon production, resulting in enhanced selectivity for the gasoline fraction. In situ XPS experiments show the possible electron transfer from cobalt to carbon and the blockage of metallic cobalt sites, which is responsible for the deactivation of the catalyst. DFT calculations reveal that the activation barrier (Ea) of methane formation decreases by 0.61 eV on the carbon-absorbed Co(111) surface, whereas the Ea of the CH + CH coupling reaction changes unnoticeably. Hydrogenation of CHx to methane becomes the preferable route among the elementary reactions on the Co(111) surface, leading to dramatic changes in the product distribution. Detailed coke-induced deactivation mechanisms of Co-based catalysts during FTS are discussed.

Atomistic theory of Ostwald ripening and disintegration of supported metal particles under reaction conditions.

Understanding Ostwald ripening and disintegration of supported metal particles under operating conditions has been of central importance in the study of sintering and dispersion of heterogeneous catalysts for long-term industrial implementation. To achieve a quantitative description of these complicated processes, an atomistic and generic theory taking into account the reaction environment, particle size and morphology, and metal-support interaction is developed. It includes (1) energetics of supported metal particles, (2) formation of monomers (both the metal adatoms and metal-reactant complexes) on supports, and (3) corresponding sintering rate equations and total activation energies, in the presence of reactants at arbitrary temperature and pressure. The thermodynamic criteria for the reactant assisted Ostwald ripening and induced disintegration are formulated, and the influence of reactants on sintering kinetics and redispersion are mapped out. Most energetics and kinetics barriers in the theory can be obtained conveniently by first-principles theory calculations. This allows for the rapid exploration of sintering and disintegration of supported metal particles in huge phase space of structures and compositions under various reaction environments. General strategies of suppressing the sintering of the supported metal particles and facilitating the redispersions of the low surface area catalysts are proposed. The theory is applied to TiO(2)(110) supported Rh particles in the presence of carbon monoxide, and reproduces well the broad temperature, pressure, and particle size range over which the sintering and redispersion occurred in such experiments. The result also highlights the importance of the metal-carbonyl complexes as monomers for Ostwald ripening and disintegration of supported metal catalysts in the presence of CO.

Crystallographic dependence of CO activation on cobalt catalysts: HCP versus FCC.

Identifying the structure sensitivity of catalysts in reactions, such as Fischer-Tropsch synthesis from CO and H2 over cobalt catalysts, is an important yet challenging issue in heterogeneous catalysis. Based on a first-principles kinetic study, we find for the first time that CO activation on hexagonal close-packed (HCP) Co not only has much higher intrinsic activity than that of face centered-cubic (FCC) Co but also prefers a different reaction route, i.e., direct dissociation with HCP Co but H-assisted dissociation on the FCC Co. The origin is identified from the formation of various denser yet favorable active sites on HCP Co not available for FCC Co, due to their distinct crystallographic structure and morphology. The great dependence of the activity on the crystallographic structure and morphology of the catalysts revealed here may open a new avenue for better, stable catalysts with maximum mass-specific reactivity.

Platinum-modulated cobalt nanocatalysts for low-temperature aqueous-phase Fischer-Tropsch synthesis.

Fischer-Tropsch synthesis (FTS) is an important catalytic process for liquid fuel generation, which converts coal/shale gas/biomass-derived syngas (a mixture of CO and H2) to oil. While FTS is thermodynamically favored at low temperature, it is desirable to develop a new catalytic system that could allow working at a relatively low reaction temperature. In this article, we present a one-step hydrogenation-reduction route for the synthesis of Pt-Co nanoparticles (NPs) which were found to be excellent catalysts for aqueous-phase FTS at 433 K. Coupling with atomic-resolution scanning transmission electron microscopy (STEM) and theoretical calculations, the outstanding activity is rationalized by the formation of Co overlayer structures on Pt NPs or Pt-Co alloy NPs. The improved energetics and kinetics from the change of the transition states imposed by the lattice mismatch between the two metals are concluded to be the key factors responsible for the dramatically improved FTS performance.

An early warning signal for grassland degradation on the Qinghai-Tibetan Plateau.

Intense grazing may lead to grassland degradation on the Qinghai-Tibetan Plateau, but it is difficult to predict where this will occur and to quantify it. Based on a process-based ecosystem model, we define a productivity-based stocking rate threshold that induces extreme grassland degradation to assess whether and where the current grazing activity in the region is sustainable. We find that the current stocking rate is below the threshold in ~80% of grassland areas, but in 55% of these grasslands the stocking rate exceeds half the threshold. According to our model projections, positive effects of climate change including elevated CO2 can partly offset negative effects of grazing across nearly 70% of grasslands on the Plateau, but only in areas below the stocking rate threshold. Our analysis suggests that stocking rate that does not exceed 60% (within 50% to 70%) of the threshold may balance human demands with grassland protection in the face of climate change.

Boosting CO hydrogenation towards C2+ hydrocarbons over interfacial TiO2-x/Ni catalysts.

Considerable attention has been drawn to tune the geometric and electronic structure of interfacial catalysts via modulating strong metal-support interactions (SMSI). Herein, we report the construction of a series of TiO2-x/Ni catalysts, where disordered TiO2-x overlayers immobilized onto the surface of Ni nanoparticles (~20 nm) are successfully engineered with SMSI effect. The optimal TiO2-x/Ni catalyst shows a CO conversion of ~19.8% in Fischer-Tropsch synthesis (FTS) process under atmospheric pressure at 220 °C. More importantly, ~64.6% of the product is C2+ paraffins, which is in sharp contrast to the result of the conventional Ni catalyst with the main product being methane. A combination study of advanced electron microscopy, multiple in-situ spectroscopic characterizations, and density functional theory calculations indicates the presence of Niδ-/TiO2-x interfacial sites, which could bind carbon atom strongly, inhibit methane formation and facilitate the C-C chain propagation, lead to the production of C2+ hydrocarbon on Ni surface.

Atomically dispersed Ir/α-MoC catalyst with high metal loading and thermal stability for water-promoted hydrogenation reaction.

Synthesis of atomically dispersed catalysts with high metal loading and thermal stability is challenging but particularly valuable for industrial application in heterogeneous catalysis. Here, we report a facile synthesis of a thermally stable atomically dispersed Ir/α-MoC catalyst with metal loading as high as 4 wt%, an unusually high value for carbide supported metal catalysts. The strong interaction between Ir and the α-MoC substrate enables high dispersion of Ir on the α-MoC surface, and modulates the electronic structure of the supported Ir species. Using quinoline hydrogenation as a model reaction, we demonstrate that this atomically dispersed Ir/α-MoC catalyst exhibits remarkable reactivity, selectivity and stability, for which the presence of high-density isolated Ir atoms is the key to achieving high metal-normalized activity and mass-specific activity. We also show that the water-promoted quinoline hydrogenation mechanism is preferred over the Ir/α-MoC, and contributes to high selectivity towards 1,2,3,4-tetrahydroquinoline. The present work demonstrates a new strategy in constructing a high-loading atomically dispersed catalyst for the hydrogenation reaction.

Estimation of late twentieth century land-cover change in California.

We present the first comprehensive multi-temporal analysis of land-cover change for California across its major ecological regions and primary land-cover types. Recently completed satellite-based estimates of land-cover and land-use change information for large portions of the United States allow for consistent measurement and comparison across heterogeneous landscapes. Landsat data were employed within a pure-panel stratified one-stage cluster sample to estimate and characterize land-cover change for 1973-2000. Results indicate anthropogenic and natural disturbances, such as forest cutting and fire, were the dominant changes, followed by large fluctuations between agriculture and rangelands. Contrary to common perception, agriculture remained relatively stable over the 27-year period with an estimated loss of 1.0% of agricultural land. The largest net declines occurred in the grasslands/shrubs class at 5,131 km2 and forest class at 4,722 km2. Developed lands increased by 37.6%, composing an estimated 4.2% of the state's land cover by 2000.

Hydroxyl improving the activity, selectivity and stability of supported Ni single atoms for selective semi-hydrogenation.

Atomically dispersed metal catalysts with high atomic utilization and selectivity have been widely studied for acetylene semi-hydrogenation in excess ethylene among others. Further improvements of activity and selectivity, in addition to stability and loading, remain elusive due to competitive adsorption and desorption between reactants and products, hydrogen activation, partial hydrogenation etc. on limited site available. Herein, comprehensive density functional theory calculations have been used to explore the new strategy by introducing an appropriate ligand to stabilize the active single atom, improving the activity and selectivity on oxide supports. We find that the hydroxyl group can stabilize Ni single atoms significantly by forming Ni1(OH)2 complexes on anatase TiO2(101), whose unique electronic and geometric properties enable high performance in acetylene semi-hydrogenation. Specifically, Ni1(OH)2/TiO2(101) shows favorable acetylene adsorption and promotes the heterolytic dissociation of H2 achieving high catalytic activity, and it simultaneously weakens the ethylene bonding to facilitate subsequent desorption showing high ethylene selectivity. Hydroxyl stabilization of single metal atoms on oxide supports and promotion of the catalytic activity are sensitive to transition metal and the oxide supports. Compared to Co, Rh, Ir, Pd, Pt, Cu, Ag and Au, and anatase ZrO2, IrO2 and NbO2 surfaces, the optimum interactions between Ni, O and Ti and resulted high activity, selectivity and stability make Ni1(OH)2/TiO2(101) a promising catalyst in acetylene hydrogenation. Our work provides valuable guidelines for utilization of ligands in the rational design of stable and efficient atomically dispersed catalysts.