Non-traditional lipid-inflammatory parameters estimate the risk of stroke in middle-aged and older Chinese adults: a nationwide prospective cohort study.
Authors: Huang X, Li C, Zeng P, Ling Y, Tan S, Bai Z, Shen S, Chen S, Nie B, Wang H, Lyu J
Journal: Journal of advanced research
bipolar disorder
mental health
open access
Abstract
Multi‐electron hydrogenation reactions, such as the reductions of N, NO to NH [, , , , , , ], and CO to fuels [, , ], are pivotal for sustainable energy systems, green fertilizer production, and restoring elemental cycles [, ]. These electrochemical processes convert abundant small molecules into value‐added products using renewable electricity []. Among them, electrochemical nitrate reduction to ammonia (NORR) is particularly attractive as it offers a sustainable alternative to the Haber–Bosch process, which consumes ∼1%–2% of global energy and emits large amounts of CO [, , , ], while simultaneously mitigating nitrate pollution []. However, like other multi‐electron hydrogenation reactions, NORR involves complex PCET steps and multiple intermediates [, ], which makes it difficult to achieve high selectivity. Recent advances highlight that the adsorption mode of N‐O intermediates plays a decisive role: promoting N‐O* adsorption over O─O* pathways enhances NH selectivity by suppressing hydrogen evolution [, , ]. Moreover, the hydrogenation of intermediates requires abundant surface H*, while HER competes for the same protons and electrons [, ]. Crucially, decoupling the adsorption site from the electron transfer site by separating where reactants or intermediates bind from where electron and proton delivery occurs enables directional electron flow, facilitates reaction pathway tuning by selectively stabilizing or accelerating desired intermediate transitions, and avoids site poisoning. Therefore, constructing integrated catalytic microenvironments that spatially co‐locate H* generation domains with neighboring electron‐rich centers for directional intermediate activation is essential. Such tandem or multifunctional systems improve PCET efficiency and product selectivity by orchestrating active hydrogen supply and oriented binding/activation of intermediates. Such designs are therefore critical for overcoming key bottlenecks in NORR and other multi‐electron hydrogenation reactions. The key challenge lies in precisely designing such reaction sites for efficient multi‐electron nitrate reduction. Here, based on crystal field theory and Lewis acid‐base principles [, , ], we modulated the d‐band center and t electrons of tetrahedral sites in the CoFeO spinel structure, successfully activating them as surface H* adsorption centers. Guided by the Hard soft acids bases (HSAB) principle [], we constructed a dual‐metal‐site system featuring decoupled adsorption and activation functions: Octahedral Co sites, as moderate Lewis acids, favor nitrogen coordination, forming stable Co─N bonds that stabilize intermediates (*NO and *NO), while octahedral Fe sites, acting as strong Lewis acids, preferentially bind hard‐base oxygen to form Fe─O bonds with antibonding properties that enable directional electron flow and promote N─O bond cleavage and protonation. The resulting FeFeCoO catalyst exhibits outstanding NO
RR performance, achieving >98% Faradaic efficiency (FE) across a wide potential range (−0.1 to –0.6 V vs. RHE), a high energy efficiency (EE) of 48.4%, and a peak NH yield rate of 1.89 × 10
mol s
cm
with 96.6% FE and 30.5% EE, which is far surpassing NRR (∼1%). It also shows remarkable stability at 0.5 A cm
for 265 h with a degradation rate of only 0.25 mV h
and, long‐term durability in Zn─NO
batteries at 1 mA cm
for 500 h. The superior robustness is attributed to contract stress that stabilizes both active sites and the surface‐H sites. This strategy can be extended to other multi‐electron hydrogenation reactions. Figure illustrates our proposed catalytic microenvironment with three functionally orthogonal sites: (i) *H generation, (ii) intermediates (*NO and *NO) adsorption, and (iii) decoupled electron‐rich activation, the latter enabling reduction catalysis while cooperatively enhancing adsorption. In theory, such integration can be achieved using multi‐atomic site catalysts. However, in practice, this type of microenvironment tends to form randomly and uncontrollably within these systems (Figure ).
RR performance, achieving >98% Faradaic efficiency (FE) across a wide potential range (−0.1 to –0.6 V vs. RHE), a high energy efficiency (EE) of 48.4%, and a peak NH yield rate of 1.89 × 10
mol s
cm
with 96.6% FE and 30.5% EE, which is far surpassing NRR (∼1%). It also shows remarkable stability at 0.5 A cm
for 265 h with a degradation rate of only 0.25 mV h
and, long‐term durability in Zn─NO
batteries at 1 mA cm
for 500 h. The superior robustness is attributed to contract stress that stabilizes both active sites and the surface‐H sites. This strategy can be extended to other multi‐electron hydrogenation reactions. Figure illustrates our proposed catalytic microenvironment with three functionally orthogonal sites: (i) *H generation, (ii) intermediates (*NO and *NO) adsorption, and (iii) decoupled electron‐rich activation, the latter enabling reduction catalysis while cooperatively enhancing adsorption. In theory, such integration can be achieved using multi‐atomic site catalysts. However, in practice, this type of microenvironment tends to form randomly and uncontrollably within these systems (Figure ).