Operator Firing Order as the Missing Mechanism in Ethanol-to-Hydrocarbon Selectivity: Contact-Geometric Analysis of ZSM-5 and MCM-22 Zeolites
{"webpage:":[0],"Operator":[1],"Firing":[2],"Order":[3],"as":[4,216,441,545,586],"a":[5,87,141,182,236,253,349,361,367,373,519,589,628,651,673,749,797],"Mechanism":[6],"for":[7,493],"Ethanol-to-Hydrocarbon":[8],"Selectivity:":[9],"A":[10],"Contact-Geometric":[11],"Analysis":[12],"of":[13,81,173,181,212,308,338,342,375,502,509,604,623,701],"ZSM-5":[14,227],"and":[15,40,46,53,66,100,118,178,228,244,291,314,388,433,454,528,557,573,634,719,738,747,796],"MCM-22":[16,229],"Zeolites":[17],"Description:":[18],"Zeolite":[19],"pore":[20],"topology":[21,35],"governs":[22],"product":[23,62],"selectivity":[24,176,363,386,699,760],"in":[25,163,214,256,296,355,416,422,426,514,533,571,581,597,660,716,788,804],"ethanol":[26],"conversion":[27],"to":[28,155,395,601,681],"hydrocarbons,":[29],"yet":[30,381,420,570,769],"the":[31,73,77,109,131,135,147,159,166,171,174,194,204,239,257,279,283,288,293,319,333,343,357,376,393,396,417,436,467,475,498,506,574,624,655,661,666,683,688,711,734,754],"mechanism":[32],"by":[33,86,303,459],"which":[34,37,356,605,613],"determines":[36,189,698],"intermediates":[38],"form":[39,536],"survive":[41],"has":[42,767],"remained":[43],"unresolved:":[44],"HZSM-5":[45],"HMCM-22":[47],"have":[48],"nominally":[49],"identical":[50],"acid":[51],"chemistry":[52],"both":[54,157],"possess":[55],"10-ring":[56,106],"apertures,":[57],"but":[58],"produce":[59,360],"markedly":[60],"different":[61],"distributions,":[63],"coke":[64],"locations,":[65],"deactivation":[67],"profiles.":[68],"This":[69],"paper":[70],"proposes":[71],"that":[72,153,235,245,276,328,369,635,708],"differentiating":[74],"variable":[75],"is":[76,146,191,301,372,439,465,584],"sequential":[78],"firing":[79],"order":[80,110,188,697],"four":[82],"geometric":[83],"operations":[84],"experienced":[85],"reacting":[88],"intermediate:":[89],"Compression":[90],"(adsorption,":[91],"C),":[92],"Constraint":[93],"(aperture":[94],"gating,":[95],"K),":[96],"Folding":[97],"(branching/oligomerization/aromatization,":[98],"F),":[99],"Unfolding":[101],"(selective":[102],"desorption,":[103],"U).":[104],"ZSM-5's":[105],"channels":[107],"enforce":[108,121],"C▷K▷F▷U":[111],"(constraint":[112],"before":[113,124],"folding);":[114],"MCM-22's":[115],"12-ring":[116],"supercages":[117],"external":[119],"pockets":[120],"C▷F▷K▷U":[122],"(folding":[123],"constraint).":[125],"Version":[126,168],"3":[127],"located":[128],"exactly":[129,139,485,534],"where":[130],"order-dependence":[132,202,531],"comes":[133],"from:":[134],"aperture":[136,207,213],"gate":[137],"commutes":[138],"with":[140,158,165,269,332,449,478,640,672,687,791],"pointwise":[142],"nonlinearity,":[143],"so":[144],"it":[145,268,277,632,649,659,671,722],"fold's":[148],"inter-site":[149],"coupling":[150],"(amplitude":[151],"transport)":[152],"fails":[154],"commute,":[156],"on-site":[160],"nonlinearity":[161],"and,":[162],"consequence,":[164],"gate.":[167],"4":[169,186,409,470,694,782],"corrects":[170],"scope":[172,195],"resulting":[175],"theorem":[177,508,667],"completes":[179],"part":[180],"second":[183],"one:":[184],"Theorem":[185,220,503,510,552,607,617,693],"(\\"operator":[187],"selectivity\\")":[190],"restated":[192],"at":[193,654,710],"its":[196,261,610,641,703],"own":[197,262,642,704],"proof":[198,414,592,619,705],"actually":[199,740],"supports":[200,707],"—":[201,243,322,406,424,432,489,492,563,633,786,802],"given":[203,260,415],"two":[205,358,712,727],"specific":[206,713],"values":[208],"used,":[209],"not":[210,335,380,419,569,768],"independent":[211,305,336,700],"general,":[215],"v3":[217],"had":[218,231],"claimed.":[219,668],"5":[221],"(the":[222],"contact-geometric":[223],"scaling":[224],"law":[225],"relating":[226],"dynamics)":[230],"asserted,":[232],"without":[233,588,630],"deriving,":[234],"rescaling":[237,246,629],"preserves":[238,278],"governing":[240],"contact":[241,280,625,684],"1-form":[242,626],"formula":[247,636],"was":[248,637],"itself":[249,638],"arithmetically":[250],"backwards,":[251],"moving":[252,658],"barrier":[254,652],"feature":[255,653],"wrong":[258,656],"direction":[259,663],"stated":[263,643],"scale":[264,644],"factor.":[265],"V4":[266,669],"replaces":[267,670],"an":[270,325,402,450],"explicit":[271,326,403,451],"coordinate":[272,674],"dilation,":[273,675],"verifies":[274],"directly":[275,457,677],"form,":[281,685],"derives":[282],"correctly-directed":[284,689],"wavefunction":[285,555,690],"relation":[286],"from":[287,664,742],"WKB":[289],"correspondence,":[290],"kernel-verifies":[292],"contactomorphism":[294,507],"claim":[295,400,580,709],"Lean":[297,423,469,476,781],"4.":[298],"The":[299,462,538],"hypothesis":[300,394],"supported":[302],"five":[304,344],"published":[306],"lines":[307],"evidence":[309],"(molecular":[310],"dynamics,":[311],"operando":[312],"DRIFTS,":[313],"structural-modification":[315],"studies,":[316],"reread":[317],"through":[318],"operator-order":[320],"lens":[321],"v4":[323,720,725],"adds":[324,366,726,748],"caveat":[327,368],"these":[329],"document":[330],"consistency":[331],"framing,":[334],"confirmation":[337],"it,":[339],"since":[340],"none":[341,603],"measured":[345,385,759],"\\"operator":[346],"order\\"":[347],"directly),":[348],"reproducible":[350],"coarse-grained":[351],"nonlinear-Schrödinger":[352],"(DNLS)":[353],"simulation":[354,378,397,739,776],"orders":[359],"~35×":[362],"ratio":[364,371,757],"(v4":[365],"this":[370,582],"property":[374],"chosen":[377],"inputs,":[379],"checked":[382],"against":[383,474,518,758],"any":[384],"ratio),":[387],"seven":[389,529],"formal":[390,463,540],"theorems":[391,501,532],"connecting":[392],"model.":[398],"Every":[399],"carries":[401],"status":[404,794],"tag":[405,438],"[VERIFIED]":[407],"(Lean":[408],"kernel),":[410],"[DERIVED]":[411],"(a":[412],"complete":[413,564],"text,":[418],"formalized":[421],"new":[425,513,787,803],"v4),":[427,789],"[MODEL],":[428],"[SIMULATION],":[429],"or":[430,593,609],"[OPEN]":[431],"nothing":[434],"outside":[435],"first":[437],"presented":[440],"proved.":[442],"Three":[443,599],"falsifiable":[444],"predictions":[445],"are":[446,542,614],"derived,":[447],"each":[448],"experimental":[452],"protocol":[453],"pass/fail":[455],"criterion,":[456],"testable":[458],"contact-time":[460],"DRIFTS.":[461],"layer":[464],"machine-checked:":[466],"accompanying":[468],"development":[471],"(github.com/TOTOGT/io)":[472],"compiles":[473],"kernel,":[477],"per-theorem":[479],"axiom":[480],"audits":[481],"(#print":[482],"axioms)":[483],"showing":[484],"[propext,":[486],"Classical.choice,":[487],"Quot.sound]":[488],"no":[490],"sorryAx":[491],"all":[494],"20":[495],"verified":[496,517,676],"theorems:":[497],"three":[499],"commutation":[500],"1":[504,608],"(ZeoliteCommutation.lean),":[505],"5(i)":[511],"(ContactMorphism.lean,":[512],"v4,":[515],"independently":[516],"local":[520],"olean":[521],"v4.32":[522],"toolchain),":[523],"nine":[524],"supporting":[525],"results":[526],"(CatGT_Main.lean),":[527],"chain-level":[530],"existential":[535],"(Theorem53NonCommutativity.lean).":[537],"remaining":[539],"obligations":[541],"explicitly":[543],"tracked":[544],"open:":[546],"continuum-limit":[547],"gate/fold":[548],"non-commutation":[549],"(Theorem":[550,577],"1(iii));":[551],"5's":[553,618],"induced":[554],"correspondence":[556],"L²":[558],"norm":[559],"preservation":[560,622],"(parts":[561],"ii–iii":[562],"pen-and-paper":[565],"proofs,":[566],"tagged":[567],"[DERIVED],":[568],"Lean);":[572],"selectivity–order":[575],"bijection":[576],"7).":[578],"No":[579],"work":[583],"asserted":[585,621],"machine-verified":[587],"corresponding,":[590],"inspectable":[591],"CI":[594],"log.":[595],"Changes":[596],"v4.":[598],"corrections":[600],"v3,":[602],"touch":[606],"kernel-checked":[611,780],"results,":[612],"unchanged.":[615],"First,":[616],"sketch":[620],"under":[627],"deriving":[631],"inconsistent":[639],"factor":[645],"(k₁₂":[646],"=":[647],"4/3):":[648],"placed":[650],"coordinate,":[657],"opposite":[662],"what":[665,733,743],"(and":[678],"now":[679],"kernel-checked)":[680],"preserve":[682],"together":[686],"relation.":[691],"Second,":[692],"claimed":[695],"operator":[696],"aperture;":[702],"only":[706],"apertures":[714],"used":[715],"Theorems":[717],"2–3,":[718],"restates":[721],"accordingly.":[723],"Third,":[724],"evidentiary":[728],"caveats":[729],"(described":[730],"above)":[731],"distinguishing":[732],"paper's":[735],"literature":[736],"review":[737],"establish":[741],"they're":[744],"consistent":[745],"with,":[746],"fourth":[750],"Open":[751],"Question:":[752],"comparing":[753],"simulated":[755],"35×":[756],"data":[761],"(e.g.":[762],"Sousa":[763],"et":[764],"al.":[765],"2014)":[766],"been":[770],"done.":[771],"Files:":[772],"manuscript":[773],"(.tex/.pdf),":[774],"DNLS":[775],"code":[777],"(dm3_dnls_zeolite_simulation.py),":[778],"figures,":[779],"proofs":[783],"(ZeoliteCommutation.lean,":[784],"ContactMorphism.lean":[785],"derivations":[790],"per-claim":[792],"verification":[793],"(OPERATOR_ORDER_DERIVATIONS_AND_STATUS.md),":[795],"standalone":[798],"v3→v4":[799],"changelog":[800],"(CHANGES_v3_to_v4.md":[801],"v4).":[805]}
Authors
- Pablo Nogueira Grossi (ORCID: https://orcid.org/0009-0000-6496-2186)
Institutions
- GfK (United States) (US)
Publication Details
- Journal
- Zenodo (CERN European Organization for Nuclear Research)
- Published
- 2026-09-19
- DOI
- https://doi.org/10.5281/zenodo.22849726
- Primary Topic
- Zeolite Catalysis and Synthesis
- Type
- preprint