E fficient and cost-effective electrocatalysts play critical roles in energy conversion and storage [1][2][3] . Homogeneous and heterogeneous catalysts represent two parallel frontiers of electrocatalysts, each with their own merits and drawbacks 4,5 . Homogeneous catalysts are attractive for their highly uniform active sites, tunable coordination environment and maximized atom utilization efficiency, but are limited by their relatively poor stability and recyclability. Heterogeneous catalysts are appealing for their high durability, excellent recyclability, and easy immobilization and integration with electrodes, but usually have rather low atom utilization efficiency due to the limited surface sites accessible to reactants. To this end, considerable efforts have been devoted to developing nanoscale heterogeneous catalysts that can increase the exposed surface atoms 3 . However, the inhomogeneity in the distribution of particle sizes and facets poses a serious challenge for controlling active sites and fundamental mechanistic studies 6,7 . In contrast, homogeneous catalysts typically exhibit the well-defined atomic structure with tunable coordination environment that is essential for deciphering the catalytic reaction pathway and rational design of targeted catalysts with tailored catalytic properties 8 . Single-atom catalysts (SACs) with monodispersed single atoms supported on solid substrates are recently emerging as an exciting class of catalysts that combine the merits of both homogeneous and heterogeneous catalysts [9][10][11][12][13][14] . However, most SACs studied to date employ metal oxides (for example, TiO 2 , CeO 2 and FeO x ) as supporting substrates to prevent atom aggregation [15][16][17][18] , which cannot be readily applied in electrocatalytic applications due to their low electrical conductivity and/or poor stability in harsh liquid-phase electrolytes (for example, strong acid or base). Atomic transitionmetal-nitrogen moieties supported in carbon (M-N-Cs) represent a unique class of SACs with high electrical conductivity and superior (electro)chemical stability for electrocatalytic applications 19 . In particular, Fe-based M-N-Cs have been extensively studied as electrocatalysts towards the oxygen reduction reaction (ORR) with demonstrated activity and stability approaching those of commercial Pt/C catalysts 20,21 . In addition, as suggested by numerous theoretical studies, M-N-Cs are promising candidates for catalysing a wide range of electrochemical processes, such as hydrogen reduction/oxidation 22 , CO 2 /CO reduction 23 and N 2 reduction 24 . A significant advantage of SACs is that the well-defined single atomic site could allow precise understanding of the catalytic reaction pathway, and rational design of targeted catalysts with tailored activity (in a manner similar to homogeneous catalyst design). However, this perceived advantage has been investigated theoretically

Belowground microbial communities strongly influence ecosystem function such that predicting function may rely on understanding ecological processes that assemble communities. Uncertainty remains, however, in what governs the relative contributions of different ecological processes. To help fill this knowledge gap, we test the general hypothesis that both initial state and degree of change in environmental conditions govern the relative contributions of different ecological assembly processes. To do so, we leveraged regional‐scale nutrient and organic matter addition experiments and used soil organic matter (SOM) as a proxy of integrated soil environmental conditions. Consistent with our hypothesis, we found that both the initial amount of SOM and the degree of change in SOM—in response to nutrient addition—influenced the relative contributions of different ecological assembly processes. These influences were most clearly observed at the regional scale, suggesting potential scale dependence. More specifically, nutrient additions homogenized bacterial community composition due to enhanced influences of homogenizing dispersal when SOM content was initially high. In contrast, nutrient additions led to divergence in community composition due to variable selection when initial SOM was low and/or when SOM increased significantly in response to nutrient additions. Our findings indicate important connections among initial conditions, degree of change in environmental variables and microbial community assembly processes that may influence ecosystem processes. These conceptual inferences highlight a need to strengthen connections between ecological theory and biogeochemical modelling.

Rice paddy fields are characterized by regular flooding and nitrogen fertilization, but the functional importance of aerobic ammonia oxidizers and nitrite oxidizers under unique agricultural management is poorly understood. In this study, we report the differential contributions of ammonia-oxidizing archaea (AOA), bacteria (AOB) and nitrite-oxidizing bacteria (NOB) to nitrification in four paddy soils from different geographic regions (Zi-Yang (ZY), Jiang-Du (JD), Lei-Zhou (LZ) and Jia-Xing (JX)) that are representative of the rice ecosystems in China. In urea-amended microcosms, nitrification activity varied greatly with 11.9, 9.46, 3.03 and 1.43 μg NO3−-N g−1 dry weight of soil per day in the ZY, JD, LZ and JX soils, respectively, over the course of a 56-day incubation period. Real-time quantitative PCR of amoA genes and pyrosequencing of 16S rRNA genes revealed significant increases in the AOA population to various extents, suggesting that their relative contributions to ammonia oxidation activity decreased from ZY to JD to LZ. The opposite trend was observed for AOB, and the JX soil stimulated only the AOB populations. DNA-based stable-isotope probing further demonstrated that active AOA numerically outcompeted their bacterial counterparts by 37.0-, 10.5- and 1.91-fold in 13C-DNA from ZY, JD and LZ soils, respectively, whereas AOB, but not AOA, were labeled in the JX soil during active nitrification. NOB were labeled to a much greater extent than AOA and AOB, and the addition of acetylene completely abolished the assimilation of 13CO2 by nitrifying populations. Phylogenetic analysis suggested that archaeal ammonia oxidation was predominantly catalyzed by soil fosmid 29i4-related AOA within the soil group 1.1b lineage. Nitrosospira cluster 3-like AOB performed most bacterial ammonia oxidation in the ZY, LZ and JX soils, whereas the majority of the 13C-AOB in the JD soil was affiliated with the Nitrosomona communis lineage. The 13C-NOB was overwhelmingly dominated by Nitrospira rather than Nitrobacter. A significant correlation was observed between the active AOA/AOB ratio and the soil oxidation capacity, implying a greater advantage of AOA over AOB under microaerophilic conditions. These results suggest the important roles of soil physiochemical properties in determining the activities of ammonia oxidizers and nitrite oxidizers.