《科學》（20240510出版）一周論文導讀

編譯 | 未玖

Science, 10 MAY 2024, VOL 384, ISSUE 6696

《科學》2024年5月10日，第384卷，6696期

天文學Astronomy

Isotopic evidence of long-lived volcanism on Io

木衛一長期火山活動的同位素證據

▲ 作者：KATHERINE DE KLEER, ERY C. HUGHES, FRANCIS NIMMO, JOHN EILER, AMY E. HOFMANN, STATIA LUSZCZ-COOK, ET AL.

▲ 連結：

https://www.science.org/doi/10.1126/science.adj0625

▲ 摘要：

木衛一上有大量的火山活動，由潮汐加熱驅動。木衛一揮發性化學元素（包括硫和氯）的同位素組成反映了其放氣和品質損失的曆史，進而記錄了演化資訊。

研究組利用對木衛一大氣層的亞毫米觀測來測量氣态二氧化硫和一氧化硫中的硫同位素，以及氣态氯化鈉和氯化鉀中的氯同位素。

結果發現34S/32S = 0.0595±0.0038（相當于δ34S = +347±86‰），與太陽系的平均值相比高度富集，這表明木衛一已經損失了94~99%的可用硫。測量還發現37Cl/35Cl = 0.403±0.028（δ37Cl = +263±88‰），表明氯也同樣富集。

這些結果表明，木衛一在其大部分（或全部）曆史中都有火山活動，早期可能有更高的放氣率和品質損失率。

▲ Abstract：

Jupiter’s moon Io hosts extensive volcanism, driven by tidal heating. The isotopic composition of Io’s inventory of volatile chemical elements, including sulfur and chlorine, reflects its outgassing and mass-loss history and thus records information about its evolution. We used submillimeter observations of Io’s atmosphere to measure sulfur isotopes in gaseous sulfur dioxide and sulfur monoxide, and chlorine isotopes in gaseous sodium chloride and potassium chloride. We find 34S/32S = 0.0595 ± 0.0038 (equivalent to δ34S = +347 ± 86‰), which is highly enriched compared to average Solar System values and indicates that Io has lost 94 to 99% of its available sulfur. Our measurement of 37Cl/35Cl = 0.403 ± 0.028 (δ37Cl = +263 ± 88‰) shows that chlorine is similarly enriched. These results indicate that Io has been volcanically active for most (or all) of its history, with potentially higher outgassing and mass-loss rates at earlier times.

材料科學Materials Science

Catalog of topological phonon materials

拓撲聲子材料目錄

▲ 作者：YUANFENG XU, M. G. VERGNIORY, DA-SHUAI MA, JUAN L. MAÑES, ZHI-DA SONG, B. ANDREI BERNEVIG, ET AL.

▲ 連結：

https://www.science.org/doi/10.1126/science.adf8458

▲ 摘要：

聲子在固态系統的許多特性中起着至關重要的作用，人們期望拓撲聲子可導緻豐富和非正常的實體特性。

在現有聲子材料資料庫的基礎上，研究組彙編了1萬多種三維晶體材料的拓撲聲子帶目錄。利用拓撲量子化學計算了聲子資料庫中材料的每組孤立聲子帶的能帶表示、相容關系和能帶拓撲。

此外還計算了所有拓撲平凡帶的實空間不變量，并将其分類為原子能帶或受阻原子能帶。研究組已選擇了1000多種“理想”的非平凡聲子材料用于未來實驗分析。這些資料集将被用于建立拓撲聲子資料庫。

▲ Abstract：

Phonons play a crucial role in many properties of solid-state systems, and it is expected that topological phonons may lead to rich and unconventional physics. On the basis of the existing phonon materials databases, we have compiled a catalog of topological phonon bands for more than 10,000 three-dimensional crystalline materials. Using topological quantum chemistry, we calculated the band representations, compatibility relations, and band topologies of each isolated set of phonon bands for the materials in the phonon databases. Additionally, we calculated the real-space invariants for all the topologically trivial bands and classified them as atomic or obstructed atomic bands. We have selected more than 1000 “ideal” nontrivial phonon materials to motivate future experiments. The datasets were used to build the Topological Phonon Database.

The odd-number cyclo[13]carbon and its dimer, cyclo[26]carbon

奇數環[13]碳及其二聚體環[26]碳

▲ 作者：FLORIAN ALBRECHT, IGOR RONČEVIĆ, YUEZE GAO, FABIAN PASCHKE, ALBERTO BAIARDI, IVANO TAVERNELLI, ET AL.

▲ 連結：

https://www.science.org/doi/10.1126/science.ado1399

▲ 摘要：

N個碳原子的分子環（環[N]碳，或CN）是測試量子化學理論方法的優秀基準系統，也是其他富碳材料有價值的前體。奇數—N環碳迄今為止一直難以捉摸，預計比偶數—N環碳更不穩定。

研究組報道了用掃描探針顯微鏡尖端操縱十氯芴在表面合成環[13]碳，C13。通過實驗和理論模拟表征了C13的性質。C13采用三重态基态和扭結幾何結構的開殼構型，根據分子環境的不同表現出不同程度的扭曲和卡賓局域化。

此外，研究組制備并表征了C13二聚體，即環[26]碳，證明了環碳及其前體作為碳同素異形體建構塊的潛力。

▲ Abstract：

Molecular rings of N carbon atoms (cyclo[N]carbons, or CN) are excellent benchmarking systems for testing quantum chemical theoretical methods and valuable precursors to other carbon-rich materials. Odd-N cyclocarbons, which have been elusive to date, are predicted to be even less stable than even-N cyclocarbons. We report the on-surface synthesis of cyclo[13]carbon, C13, by manipulation of decachlorofluorene with a scanning probe microscope tip. We elucidated the properties of C13 by experiment and theoretical modeling. C13 adopts an open-shell configuration with a triplet ground state and a kinked geometry, which shows different extents of distortion and carbene localization depending on the molecular environment. Moreover, we prepared and characterized the C13 dimer, cyclo[26]carbon, demonstrating the potential of cyclocarbons and their precursors as building blocks for carbon allotropes.

化學Chemistry

Atomically dispersed hexavalent iridium oxide from MnO2 reduction for oxygen evolution catalysis

MnO2還原的原子分散六價氧化銥助力析氧催化

▲ 作者：AILONG LI, SHUANG KONG, KIYOHIRO ADACHI, HIDESHI OOKA, KAZUNA FUSHIMI, QIKE JIANG, ET AL.

▲ 連結：

https://www.science.org/doi/10.1126/science.adg5193

▲ 摘要：

人們預測六價氧化銥（IrVI）在酸中的析氧反應中比其他氧化銥更具活性、更穩定；然而其實驗實作仍頗具挑戰性。

研究組報道了用于質子交換膜（PEM）水電解的原子分散IrVI氧化物（IrVI-ado）的合成、表征和應用。用氧化錳（MnO2）氧化取代六氯銥酸鉀（K2IrCl6）配體，合成了IrVI-ado。

IrVI-ado的品質比活度（1.7×105 A/gIr）和周轉率（1.5×108）超過了基準銥氧化物，PEM操作期間的原位X射線分析表明，IrVI在電流密度高達2.3 A/cm2時仍具備耐久性。IrVI-ado的高活性和穩定性顯示了其作為PEM電解陽極材料的前景。

▲ Abstract：

Hexavalent iridium (IrVI) oxide is predicted to be more active and stable than any other iridium oxide for the oxygen evolution reaction in acid; however, its experimental realization remains challenging. In this work, we report the synthesis, characterization, and application of atomically dispersed IrVI oxide (IrVI-ado) for proton exchange membrane (PEM) water electrolysis. The IrVI-ado was synthesized by oxidatively substituting the ligands of potassium hexachloroiridate(IV) (K2IrCl6) with manganese oxide (MnO2). The mass-specific activity (1.7 × 105 amperes per gram of iridium) and turnover number (1.5 × 108) exceeded those of benchmark iridium oxides, and in situ x-ray analysis during PEM operations manifested the durability of IrVI at current densities up to 2.3 amperes per square centimeter. The high activity and stability of IrVI-ado showcase its promise as an anode material for PEM electrolysis.

Scalable decarboxylative trifluoromethylation by ion-shielding heterogeneous photoelectrocatalysis

離子屏蔽非均相光電催化助力可擴充脫羧三氟甲基化

▲ 作者：YIXIN CHEN, YUCHEN HE, YONG GAO, JIAKUN XUE, WEI QU, JUN XUAN AND YIMING MO

▲ 連結：

https://www.science.org/doi/10.1126/science.adm8902

▲ 摘要：

電化學為增值精細化學品提供了可持續的合成途徑，但通常受到電極和不同于靶位點的氧化還原敏感功能性之間競争電子轉移的限制。

研究組描述了一種離子屏蔽的非均相光電催化政策，以施加傳質限制，進而逆轉了熱力學決定的電子轉移順序。使用三氟乙酸鹽（一種廉價但相對惰性的三氟甲基（CF3）源）展示了該政策可實作敏感（雜）芳烴的脫羧三氟甲基化。

由三氟乙酸根陰離子靜電吸附在正钼摻雜的三氧化鎢（WO3）光陽極上形成的離子屏蔽層，可防止基底和光生空穴之間無益的電子轉移。通過利用光電化學流動電池實作穩健的光陽極穩定性（約380小時）、良好的基底範圍，以及100克合成的可擴充能力，充分證明了該政策的實用性。

▲ Abstract：

Electrochemistry offers a sustainable synthesis route to value-added fine chemicals but is often constrained by competing electron transfer between the electrode and redox-sensitive functionalities distinct from the target site. Here, we describe an ion-shielding heterogeneous photoelectrocatalysis strategy to impose mass-transfer limitations that invert the thermodynamically determined order of electron transfer. This strategy is showcased to enable decarboxylative trifluoromethylation of sensitive (hetero)arenes by using trifluoroacetate, an inexpensive yet relatively inert trifluoromethyl group (CF3) source. An ion-shielding layer, formed by trifluoroacetate anions electrostatically adsorbed on a positive molybdenum-doped tungsten trioxide (WO3) photoanode, prevents undesired electron transfer between substrates and photogenerated holes. The practicality of the developed method was demonstrated with robust photoanode stability (approximately 380 hours), a good substrate scope, and scaling capability to achieve 100-gram synthesis by using photoelectrochemical flow cells.

地球科學Earth Science

A diminished North Atlantic nutrient stream during Younger Dryas climate reversal

新仙女木期氣候逆轉期間北大西洋營養流減少

▲ 作者：JEAN LYNCH-STIEGLITZ, TYLER D. VOLLMER, SHANNON G. VALLEY, ERIC BLACKMON, SIFAN GU AND THOMAS M. MARCHITTO

▲ 連結：

https://www.science.org/doi/10.1126/science.adi5543

▲ 摘要：

北大西洋的高生物生産力由通過墨西哥灣流（營養流）向該地區平流供應的營養物質所刺激。有人提出，預計未來大西洋經向翻轉環流（AMOC）的下降将導緻營養物質供應減少，進而導緻生産力下降。

研究組分析了标志着從末次冰期過渡的新仙女木期氣候逆轉期間營養流是如何變化的。在AMOC減弱期間，佛羅裡達海峽的墨西哥灣流營養物質含量下降，氧含量增加。營養流的減少伴随着北大西洋高緯度地區生物生産力的下降，這支援了理論和模組化研究中所假設的聯系。

▲ Abstract：

The high rate of biological productivity in the North Atlantic is stimulated by the advective supply of nutrients into the region via the Gulf Stream (nutrient stream). It has been proposed that the projected future decline in the Atlantic Meridional Overturning Circulation (AMOC) will cause a reduction in nutrient supply and resulting productivity. In this work, we examine how the nutrient stream changed over the Younger Dryas climate reversal that marked the transition out of the last ice age. Gulf Stream nutrient content decreased, and oxygen content increased at the Florida Straits during this time of weakened AMOC. The decreased nutrient stream was accompanied by a reduction in biological productivity at higher latitudes in the North Atlantic, which supports the link postulated in theoretical and modeling studies.